JPH11246573A - Fluoroalkyl group-containing phosphonate oligomers and their production, and surfactant and resin composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce new compounds having excellent water and oil repellency and antifouling property, useful as a nonaqueous system surfactant and utilizable as a vesicular agent, an auxiliary for medicines and agrochemicals, a medical material, etc., having high stability. SOLUTION: The compounds represented by formula I R<1> and R<2> are each (CF<2> )n Y [Y is H, F or the like; (n) is 1-10] or the like; R<3> is H or methyl; R<4> and R<5> are each a 1-8C alkyl; (m) is 1-100}, are obtained by reacting fluoroalkanoyl peroxides represented by formula II with a phosphonate compound represented by formula III and having a vinyl group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel fluoroalkyl group-containing phosphonate oligomer, a method for producing the same, a non-aqueous surfactant containing the same, and a resin having excellent water / oil / oil repellency and stain resistance. Composition.

[0002]

2. Description of the Related Art Fluoroalkyl group-containing compounds have attracted attention as compounds exhibiting useful properties such as light resistance, water / oil repellency, and physiological activity. It has been widely known that fluoroalkyl group-containing carboxylic acids such as perfluorooctanoic acid exhibit high interfacial properties in an aqueous solution. Examples of the non-aqueous fluorine surfactant include alkyl perfluoroalkanecarboxylates, fluorine surfactants obtained by oligomerization of hexafluoropropene oxide, and polyfluoroacylbenzenes obtained by a Friedel-Crafts reaction with benzene. Has been proposed.

[0003] However, since known fluorine-based surfactants are compounds composed only of a hydrophilic group and a water-repellent group, excellent properties due to fluorine atoms, such as water and oil repellency, can be obtained in various environments. Was difficult to express. In the field of surfactants, surfactants in which fluorine, especially long-chain fluoroalkyl groups have been introduced, may have superior performance due to fluorine as compared to conventional hydrocarbon surfactants. Attention has been paid to low molecular weight surfactants. However,
There is almost no knowledge of high molecular weight surfactants into which fluoroalkyl groups have been introduced.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a novel fluoroalkyl group-containing phosphonate oligomer having water / oil repellency and high surface activity, a process for producing the same, and a process for producing the same. And a resin composition having excellent water and oil repellency and antifouling property.

[0005]

Under such circumstances, the present inventors have conducted intensive studies and as a result, by reacting a specific fluoroalkanoyl peroxide with a phosphonate compound having a vinyl group, a novel fluoroalkyl group has been obtained. A phosphonate-containing oligomer was obtained, and it was found that a surfactant and a resin composition containing the same as an active ingredient could solve the above-mentioned problems, and completed the present invention.

That is, the present invention provides the following general formula (1):

[0007]

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In the formula, R ¹ and R ² are the same or different and are (CF ₂ ) _n Y or CF (CF ₃ )-[OCF ₂ CF
(CF ₃ )] _p -OC ₃ F ₇ (wherein, Y represents a hydrogen atom, a fluorine atom or a chlorine atom, n represents an integer of 1 to 10, and p represents an integer of 0 to 10), R ³ represents a hydrogen atom or a methyl group; R ⁴ and R ⁵ are the same or different;
Shows a linear or branched alkyl group having 1 to 8 carbon atoms,
m shows 1-100. And a fluoroalkyl group-containing phosphonate oligomer represented by｝.

Further, the present invention provides the following general formula (2):

[0010]

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(Wherein R ¹ and R ² are as defined above), and a fluoroalkanoyl peroxide represented by the following general formula (3):

[0012]

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(Wherein R ³ , R ⁴ and R ⁵ have the same meanings as described above), and are reacted with a phosphonate compound having a vinyl group represented by the following general formula (1):

[0014]

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In the formula, R ¹ and R ² are the same or different and are (CF ₂ ) _n Y or CF (CF ₃ )-[OCF ₂ CF
(CF ₃ )] _p -OC ₃ F ₇ (wherein, Y represents a hydrogen atom, a fluorine atom or a chlorine atom, n represents an integer of 1 to 10, and p represents an integer of 0 to 10), R ³ represents a hydrogen atom or a methyl group; R ⁴ and R ⁵ are the same or different;
Shows a linear or branched alkyl group having 1 to 8 carbon atoms,
m shows 1-100. The present invention provides a method for producing a fluoroalkyl group-containing phosphonate oligomer represented by｝.

Further, the present invention provides a surfactant containing a fluoroalkyl group-containing phosphonate oligomer represented by the general formula (1) as an active ingredient, and a fluoroalkyl group-containing phosphonate represented by the general formula (1). An object of the present invention is to provide a resin composition containing oligomers.

[0017]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The fluoroalkyl group-containing phosphonate oligomer according to the present invention is represented by the above general formula (1). In the formula, R ¹ and R ² are preferably those wherein, in the formula: (CF ₂ ) _n Y, n is 1 to 8, particularly 1 to 5, and Y is a fluorine atom. Also, the formula: CF
(CF ₃₎ - [OCF ₂ CF (CF _{3)] p} - OC ₃ F
_{In 7} , p is 0 to 8, particularly 0 to 6. Preferred of R ³ is a hydrogen atom or a methyl group. Specific examples of R ⁴ and R ⁵ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group, isopentyl group, n-hexyl group, isohexyl group, n -Heptyl, isoheptyl, n
-Octyl, isooctyl group and the like.
Particularly, a methyl group is preferable. The preferable range of m is 1-5.
0, particularly preferably 1 to 10. Further, in the oligomers of the general formula (1) of the present invention, R ¹ and R ²
The oligomer in which the fluoroalkyl group represented by is introduced only at one terminal of the oligomer may be contained at an arbitrary ratio.

Next, a method for producing the fluoroalkyl group-containing phosphonate oligomer represented by the general formula (1) according to the present invention will be described. Specific examples of the fluoroalkanoyl peroxide represented by the general formula (2) as a reaction raw material include diperfluoro-2-methyl-3-oxahexanoyl peroxide and diperfluoro-2,5 peroxide. -Dimethyl-3,6-dioxananoyl, diperfluoro-2,5,8-trimethyl-3, peroxide
6,9-trioxadodecanoyl, diperfluorobutyryl peroxide, diperfluoroheptanoyl peroxide, diperfluorooctanoyl peroxide and the like. As a method for producing such fluoroalkanoyl peroxides, a known method can be used.For example, a fluoroalkyl group-containing acyl halide can be added to a fluorine-containing aromatic solvent or a fluorine-containing aliphatic solvent such as CFC alternative. And hydrogen peroxide in the presence of an alkali such as sodium hydroxide, potassium hydroxide, potassium bicarbonate, sodium carbonate or potassium carbonate.

Specific examples of the phosphonate compound having a vinyl group represented by the general formula (3), which is the other reaction raw material, include dimethyl vinyl phosphonate, diethyl vinyl phosphonate, di-n-propyl vinyl phosphonate, di-isopropyl vinyl Phosphonate, di-n-butyl vinyl phosphonate, di-isobutyl vinyl phosphonate, di-n-pentyl vinyl phosphonate, di-isopentyl vinyl phosphonate, di-n-hexyl vinyl phosphonate, di-isohexyl vinyl phosphonate, di-n- Heptyl vinyl phosphonate, di-isoheptyl vinyl phosphonate, di-n-octyl vinyl phosphonate, di-isooctyl vinyl phosphonate, methyl ethyl vinyl phosphonate, methyl-n-propyl vinyl phosphonate, methyl Isopropyl vinyl phosphonate, methyl -n- butyl vinylphosphonate, ethyl -
n-Propyl vinyl phosphonate, ethyl-n-butyl vinyl phosphonate and the like.

Next, conditions for reacting the fluoroalkanoyl peroxide with the phosphonate having a vinyl group will be described. The molar ratio of the fluoroalkanoyl peroxide to the phosphonate compound having a vinyl group is generally in the range of 1: 1 to 10, preferably in the range of 1: 1.2 to 5. The reaction can be carried out at normal pressure, and the reaction temperature is usually −20 to 150 ° C., preferably 0 to 100 ° C. If the reaction temperature is lower than −20 ° C., the reaction tends to take a long time. On the other hand, if it exceeds 150 ° C., the pressure in the reaction system increases and the reaction operation tends to be difficult, which is not preferable. The reaction time is generally 30 minutes to 20 hours, preferably 3 to 10 hours. This reaction can be carried out without solvent, but it is preferable to carry out the reaction in a solvent in order to carry out the reaction with fluoroalkanoyl peroxides more smoothly. As the reaction solvent, a halogenated aliphatic solvent is particularly preferably used. For example, methylene chloride, chloroform, 2-chloro-1,2-dibromo-1,1,2-trifluoroethane, 1,2-dibromo Hexafluoropropane, 1,2
-Dibromotetrafluoroethane, fluorotrichloromethane, heptafluoro-2,3,3-trichlorobutane, 1,1,1,3-tetrachlorotetrafluoropropane, 1,1,2-trichlorotrifluoropropane,
1,1,2-trichlorotrifluoroethane, 1,1-
Dichloro-2,2,3,3,3-pentafluoropropane, 1,3-dichloro-1,2,2,3,3-pentafluoropropane, etc., and these may be used alone or in combination of two or more. Can be used. Among them, especially 1,
A mixed solvent of 1-dichloro-2,2,3,3,3-pentafluoropropane and 1,3-dichloro-1,2,2,3,3-pentafluoropropane is preferred. The concentration of fluoroalkanoyl peroxides in these solvents is
The content is preferably in the range of 0.5 to 30% by weight.

The fluoroalkyl group-containing phosphonate oligomers thus obtained can be purified, if desired, by conventional purification means such as dialysis, reprecipitation, recrystallization, distillation, and column chromatography.

Next, the surfactant of the present invention will be described. In the surfactant of the present invention, preferred examples of the fluoroalkyl group-containing phosphonate oligomer as an active ingredient include R ¹ and R ^{2 in the} general formula (1).
In the formula: (CF ₂ ) _n Y, n is 1 to 8, particularly 4 to 8, and Y is a fluorine atom. Also, the formula: CF (C
F ₃ )-[OCF ₂ CF (CF ₃ )] _p -OC ₃ F
_{In 7} , p is 0 to 10, particularly 2 to 10. The effect of surface activity is affected by the length of the fluoroalkyl group of R ¹ and R ^2. For example, as p in the above formula increases, the effect of surface activity tends to increase. Also, R ¹ and R
² are preferably the same group. R ³ is preferably a hydrogen atom or a methyl group, and R ⁴ and R ⁵ are preferably a methyl group having 1 to 5 carbon atoms, particularly preferably 1 to 3 carbon atoms,
It is a lower alkyl group such as an ethyl group and a propyl group, and a methyl group is particularly preferable. m is preferably 1 to 50, particularly preferably 1 to 10.

The surfactant of the present invention exhibits an excellent surfactant effect when the amount of the active ingredient is usually 0.01 g / L or more, preferably 1 g / L or more. The surfactant of the present invention can be used in a usual manner, and can be used in combination with other known surfactants. The other surfactant is not particularly limited, and includes, for example, an anionic surfactant, a nonionic surfactant, and a cationic surfactant.

Examples of the anionic surfactant include a sulfonate, a sulfate, and a carboxylate. Examples of the sulfonate-based surfactant include alkylbenzene sulfonates having 9 to 15 carbon atoms, alkyl sulfonates having 12 to 16 carbon atoms, alkenes and hydroxyalkane sulfonates, disulfonates,
α-olefin sulfonate and the like. As sulfate surfactants, tallow fatty alcohol, oleyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, monoalcohols such as primary alcohols such as stearyl alcohol or secondary alcohols such as oxo alcohols having 10 to 20 carbon atoms, sulfuric acid monoesters, Examples include hydroxycarboxylic acid, aminocarboxylic acid, hydroxysulfonic acid, aminosulfonic acid, alkylsulfosuccinic acid, sulfosuccinate, and sulfosuccinic alcohol. Also, soaps such as lauric acid, myristic acid, palmitic acid, stearic acid, coconut oil, palm kernel oil, tallow fatty acid and the like can be mentioned.

Examples of the nonionic surfactant include fatty alcohols, alkylphenols, fatty acids, fatty amines, fatty acid amides, ethylene oxide-propylene oxide block copolymers, polyethylenated carboxylic acid amides, aminooxides and sulfoxides.

Examples of the cationic surfactant include an organic acid salt or an inorganic acid salt of an aliphatic amine having at least one alkyl group having 12 to 18 carbon atoms, a quaternary ammonium salt thereof, and an aryl group such as a benzyl group. And heterocyclic quaternary ammonium salts such as aromatic quaternary ammonium salts, pyridium salts and imidazolium salts, and onium salts such as sulfonyl salts and phosphonium salts. These other surfactants may be present as organic salts such as sodium, potassium, ammonium, mono-, di- or triethanolamine. These compounds may be used alone or in combination of two or more.

As other optional components, components of ordinary detergents such as foam stabilizers, foam inhibitors, calcium complexing or precipitating agents, softening agents, alkalis or electrolytes, bleaching agents, bleaching agents Activators, redeposition inhibitors, corrosion inhibitors, bactericidal substances, enzymes, enzyme stabilizers, brighteners, colorants,
It can be used in combination with a fluorescent agent or the like. The surfactant of the present invention has excellent properties due to fluorine atoms such as water repellency and oil repellency, so it has high stability vesicles, pharmaceutical and agrochemical auxiliaries, medical materials, oxygen-enriched films, various lubricants Additives, paints, ink leveling agents, paint movers, resist strippers, foaming agents for cleaning, fiber treatment agents, fluorine resin surface modifiers, and the like.

Next, the resin composition of the present invention will be described. As preferable examples of the fluoroalkyl group-containing phosphonate oligomer contained in the resin composition of the present invention, in the general formula (1), R ¹ and R ² are represented by the formula: (C
In F ₂ ) _n Y, n is 1 to 8, especially 1 to 5, and Y is a fluorine atom. The formula: CF (CF ₃ )-[OCF
₂ CF (CF ₃ )] _p -OC ₃ F _{7 wherein} p is 0 to 10,
Particularly, it is 0 to 2. Preferably, R ¹ and R ² are the same group. Preferred of R ³ is a hydrogen atom or a methyl group. R ⁴ and R ⁵ are preferably a methyl group having 1 to 5 carbon atoms, particularly preferably 1 to 3 carbon atoms;
It is a lower alkyl group such as an ethyl group and a propyl group, and a methyl group is particularly preferable. m is preferably 1 to 50, particularly preferably 1 to 10.

As the resin applicable in the present invention,
There is no particular limitation, and when used as a rubber composition,
For example, natural rubber, styrene-butadiene rubber (SB
R), acronitrile-butadiene rubber (NBR),
Butyl rubber (IIR), polybutadiene rubber (BR),
Ethylene-propylene rubber (EPPM), chlorobutylene rubber (CR), polyisobutylene rubber, acrylic rubber, hydrogenated acrylonitrile-butadiene rubber, polysulfide rubber, urethane rubber, acrylsulfonated rubber, silicone rubber and modified products thereof And the like, and these may be a blend rubber of two or more kinds. In addition, examples of the resin serving as a matrix when obtaining a resin molded product such as a sheet, a film, a container, and a fiber include polyvinyl chloride resin, polyethylene resin, polypropylene resin, polyamide resin, polycarbonate resin, polyester resin, and polystyrene resin. , ABS resin, AS resin, thermoplastic resin such as thermoplastic acrylic resin, epoxy resin, unsaturated polyester resin, diaryl phthalate resin, phenol resin, thermosetting resin such as urea resin, alkyd resin, melanin resin, guanazine resin, Examples include a vinyl resin, an epoxy resin, a polyamine resin, an acrylic resin, a polybutadiene resin, a urethane resin, a silicon resin, a fluorine-containing resin, and modified products thereof.

The amount of the fluoroalkyl group-containing phosphonate oligomer added to the resin is usually 0.01 to 1
0% by weight, preferably 0.5 to 5% by weight. Also,
Other components include inorganic fillers such as white carbon, carbon black, zeolite, calcium carbonate, clay, barium sulfate, and magnesium carbonate, organic fillers such as high styrene resin, lignin, and phenol resin, antibacterial agents, and ultraviolet absorbers. , An antioxidant, an extender, a dispersing aid, a vulcanizing agent, a vulcanization accelerator, a vulcanizing aid, a softening agent, an antioxidant, and a plasticizer. The resin composition according to the present invention has excellent water and oil repellency and stain resistance.

[0031]

Next, the present invention will be described in more detail with reference to examples, but this is merely an example and does not limit the present invention. Example 1 2 equipped with a condenser, a thermometer, a stirrer, and a dropping funnel
In a 00 ml four-necked flask, 1.43 g (8.7 mmol) of diethyl vinylphosphonate was added to 1,1-dichloro-2,2,3,3,3.
-Pentafluoropropane and 1,3-dichloro-1,2,2,3,3
-1: 1 mixed solvent of pentafluoropropane (AK-225)
Dissolved in 40 g of diperfluorobutyryl peroxide.
36 g (3.2 mmol) were quickly added dropwise to the AK-225 solution at room temperature in a nitrogen stream. After that, heat to 40 ° C,
The mixture was stirred for 5 hours. After the reaction, the solvent was distilled off under reduced pressure, and the obtained crude product was purified by dialysis using AK-225 as a solvent. Then, by vacuum drying the residue,
1.78 g (yield 71%) of the oligomer was obtained. The average molecular weight determined by GPC was 2,300. FT-I
The fluoroalkyl group-containing phosphonate oligomer was confirmed by R, ¹ H-NMR and ¹⁹ F-NMR.

FT-IR (KBr, cm ^-1 ): 1230 (C
_{F 2), 1030 (PO)} 1 H-NMR (δ, D20): 1.16~1.48 (CH 2), 1.
60~2.22 (CH), 4.00~4.24 (CH 3), 4.24~4.50
(CH ₂ ) ¹⁹ F-NMR (δ, D20, ext. CF ₃ COOH): -4.78, -4
4.47, -52.08 Based on the above analysis results, the obtained product was sample A in Table 1.
It was confirmed to be fluoroalkyl group-containing phosphonate oligomers having the structure:

Example 2 Diethyl vinyl phosphonate 1.64 was used as a reaction raw material.
g (10 mmol), diperfluoro-2-methyl peroxide
Except that 2.17 g (3.3 mmol) of 3-oxahexanoyl was used, the synthesis was carried out in the same manner as in Example 1 to obtain 1.16 g of an oligomer (33% yield). The average molecular weight determined by GPC was 1,200. FT-IR,
^The product was confirmed by ¹ H-NMR and ¹⁹ F-NMR.

FT-IR (KBr, cm ^-1 ): 1330 (C
F ₃ ), 1240 (CF ₂ ), 1210 (P = O), 1030 (P−
O) ¹ H-NMR (δ, D20): 1.12 to 1.48 (CH ₂ ), 1.
60-2.32 (CH), 3.76-4.30 (CH ₂ , CH ₃ ) ¹⁹ F-NMR (δ, D20, ext. CF ₃ COOH): -6.80, -5
3.95 Based on the above analysis results, the obtained product was sample B in Table 1.
It was confirmed to be fluoroalkyl group-containing phosphonate oligomers having the structure:

Example 3 Diethyl vinyl phosphonate 1.25 was used as a reaction raw material.
g (7.6 mmol), 2.48 g of diperfluoro-2,5-dimethyl-3,6-dioxanonanoyl peroxide (2.
Except for using 5 mmol), synthesis was performed in the same manner as in Example 1 to obtain 2.17 g of the oligomer (yield: 62%). The average molecular weight determined by GPC was 2,400. By FT-IR, ¹ H-NMR and ¹⁹ F-NMR,
The product was confirmed.

FT-IR (KBr, cm ^-1 ): 1310 (C
F ₃ ), 1220 (CF ₂ ), 1200 (P = O), 1040 (PO) ¹ H-NMR (δ, D20): 1.20-1.
_{44 (CH 2), 1.58~2.30 (} CH), 3.60~4.02 (CH
_{3), 4.04~4.28 (CH 2)} 19 F-NMR (δ, D20, ext CF 3 COOH): -. 5.87, -5
4.13, -69.94 From the results of the analysis, it was confirmed that the obtained product was a fluoroalkyl group-containing phosphonate oligomer having the structure of Sample C in Table 1.

Example 4 As a reaction raw material, 0.89 of diethyl vinylphosphonate was used.
g (5.4 mmol), diperfluoroperoxide-2,5,8
Except that 2.51 g (1.9 mmol) of -trimethyl-3,6,9-trioxadodecanoyl was used, synthesis was performed in the same manner as in Example 1 to obtain 2.85 g of an oligomer (88% yield). . The average molecular weight determined by GPC is
1,200. FT-IR, ¹ H-NMR, ¹⁹ F-N
The product was confirmed by MR.

FT-IR (KBr, cm ^-1 ): 1310 (C
F ₃ ), 1240 (CF ₂ ), 1210 (P = O), 1050 (P−
O) ¹ H-NMR (δ, D20): 1.22 to 1.46 (CH ₂ ), 1.
62~2.32 (CH), 4.04~4.24 (CH 3), 4.24~4.64
^{_{(CH 2) 19 F-NMR}} (δ, D20, ext CF 3 COOH.): - 7.03, -5
4.26, -69.63 Based on the above analysis results, the obtained product was sample D in Table 1.
It was confirmed to be fluoroalkyl group-containing phosphonate oligomers having the structure:

[0039]

[Table 1]

(Evaluation as Surfactant) Examples 1-4
The solubility of the fluoroalkyl group-containing phosphonate oligomers of Samples A to D obtained in above in various solvents was tested. The results are shown in Table 2. In the table, ○ indicates “very soluble”, Δ indicates “not very soluble”, and X indicates “not soluble at all”. Further, the fluoroalkyl group-containing phosphonate oligomers of Samples BD obtained in Examples 2 to 4 were allowed to stand at 25 ° C overnight, and then dissolved in m-xylene to prepare samples having various concentrations. The surface tension of each sample was measured at a constant temperature of 30 ° C. using a surface tensiometer. The result is shown in FIG.

[0041]

[Table 2]

(Water and oil repellency test) Examples 1 to 4 (Sample A
Fluoroalkyl group-containing phosphonate oligomers obtained in (1) to (D) are converted to polymethyl methacrylate (PMMA).
A mixture of 0.98 g and 1% by weight was dissolved in 30 ml of tetrahydrofuran (THF) and placed in a petri dish having a diameter of 5 cm. After removing THF by air drying,
After drying in vacuum for 24 hours, the contact angles of dodecane and water were measured. Table 3 shows the results. Contact angle measurement is ER
A goniometer G-1 manufactured by MA was used. In addition, PMM
The blank in which the fluoroalkyl group-containing phosphonium oligomer of the present invention was not added to A was used as a blank.

[0043]

[Table 3]

[0044]

Industrial Applicability The fluoroalkyl group-containing phosphonate oligomers of the present invention have excellent water and oil repellency and antifouling properties due to fluorine atoms, are useful as non-aqueous surfactants, and have a high stability. High vesicles, pharmaceutical and pesticide auxiliaries,
It can be used as a medical material, an oxygen-enriched film, an additive for various lubricants, a paint, an ink leveling agent, a paint mover, a resist remover, a foaming agent for cleaning, and a fluorine resin surface modifier. Further, the resin composition of the present invention,
It has excellent water and oil repellency and antifouling properties.

[Brief description of the drawings]

FIG. 1 shows a relationship between the concentration of the oligomer of the present invention and the surface tension.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Tsutomu Watanabe 9-11-1, Kameido, Koto-ku, Tokyo Nippon Kagaku Kogyo Co., Ltd.

Claims (4)

[Claims] 1. The following general formula (1): In the formula, R ¹ and R ² are the same or different, and (CF ₂ ) _n
Y or CF (CF ₃₎ - [OCF ₂ CF (CF _{3)] p} -
OC ₃ F ₇ (wherein, Y represents a hydrogen atom, a fluorine atom or a chlorine atom, n represents an integer of 1 to 10, p represents an integer of 0 to 10), and R ³ represents a hydrogen atom or methyl R ⁴ and R ⁵ are the same or different and each have 1 to 8 carbon atoms
Represents a linear or branched alkyl group, wherein m is 1 to 10
Indicates 0. Fluoroalkyl group-containing phosphonate oligomers represented by｝. 2. The following general formula (2): (Wherein R ¹ and R ² have the same meanings as described above), and a fluoroalkanoyl peroxide represented by the following general formula (3): (Wherein R ³ , R ⁴ and R ⁵ have the same meanings as described above), and are reacted with a phosphonate compound having a vinyl group represented by the following general formula (1): In the formula, R ¹ and R ² are the same or different, and (CF ₂ ) _n
Y or CF (CF ₃₎ - [OCF ₂ CF (CF _{3)] p} -
OC ₃ F ₇ (wherein, Y represents a hydrogen atom, a fluorine atom or a chlorine atom, n represents an integer of 1 to 10, p represents an integer of 0 to 10), and R ³ represents a hydrogen atom or methyl R ⁴ and R ⁵ are the same or different and each have 1 to 8 carbon atoms
Represents a linear or branched alkyl group, wherein m is 1 to 10
Indicates 0. A method for producing a fluoroalkyl group-containing phosphonate oligomer represented by｝. 3. A surfactant comprising a fluoroalkyl group-containing phosphonate oligomer represented by the general formula (1) as an active ingredient. 4. A resin composition comprising a fluoroalkyl group-containing phosphonate oligomer represented by the general formula (1).