JP2014015523A - Acrylic acid ester polymer having excellent water and oil repellency, and method of producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymer which has high isotacticity and exhibits excellent water repellency, oil repellency and antifouling properties.SOLUTION: A polymer has a repeating unit derived from: a monomer represented by the general formula (1) defined by CH=CH-COO-X-Rf, where X represents a C1-C10 divalent aliphatic hydrocarbon group or a C6-C10 aromatic hydrocarbon group or cyclic aliphatic hydrocarbon group, and Rf represents a linear or branched C1-C6 perfluoroalkyl group; or a monomer represented by the general formula (2) defined by CH=C(CH)-COO-R, where R represents a linear or branched C10-C30 aliphatic hydrocarbon group. The stereoregularity of the main chain of the repeating unit has isotacticity of 65% or more.

Description

  The present invention relates to a crystalline polymer having a novel three-dimensional structure which is an active ingredient of a water repellent, an oil repellent, or an antifouling agent, and a method for producing the same.

  Conventionally, a fluoropolymer having a fluoroalkyl group such as a perfluoroalkyl group in the side chain generally exhibits properties such as water and oil repellency derived from the fluorine atom contained therein, and is used for paper, fiber, plastic, metal, etc. Widely used as a surface treatment agent. Among them, the fluorinated acrylate polymer is excellent in water and oil repellency, and the fluoroalkyl group of the fluorinated acrylate monomer usually has 8 or more carbon atoms.

  However, in recent years, it has been announced that compounds containing fluoroalkyl groups having 8 carbon atoms obtained by telomerization may produce perfluoro-octanoic acid (hereinafter abbreviated as “PFOA”) by decomposition or metabolism. (EPA OPPT FACT SHEET April 14, 2003 (http: //www.epa.-gov/opptintr/pfoa/pfoafacts.pdf)). The EPA (US Environmental Protection Agency) has also announced that it will strengthen scientific research against PFOA (EPA report “PRELIMINARY RISK ASSESSMENT OF THE DEVELOP-MENTAL TOXICITY ASSOCIATED WITH EXPOSURE TO PERFLUOROOCTANOIC ACID AND ITS SALTS”). (See http://www.epa.gov/opptintr/pfoa/pfoara.pdf). Thus, EPA is concerned with the bioaccumulation potential of PFOA.

  On the other hand, short-chain perfluoroalkyls having less than 8 carbon atoms, particularly those having 6 or less carbon atoms, are said to have low bioaccumulation properties. Therefore, in order to reduce the environmental burden, a fluorine-containing acrylate polymer having a short-chain perfluoroalkyl group in the side chain is required. However, the fluorine-containing acrylate polymer composed of short-chain perfluoroalkyl groups has a decreased crystallinity and no crystal melting point (Tm) as the number of fluorine atoms in the perfluoroalkyl group decreases. There is a problem that water / oil repellency cannot be obtained.

  In order to enhance the unique properties such as the water and oil repellency of the fluorine-containing acrylate polymer having 6 or less carbon atoms, the three-dimensional structure of the main chain or side chain is required to enhance the orientation of the side chain fluoroalkyl group. Need to be precisely controlled.

  Yasuda et al. Used a rare earth metal complex catalyst to polymerize a fluorine-containing (meth) acrylate having a perfluoroalkyl group in the side chain, and to have a high syndiotacticity in which the stereoregularity of the main chain was controlled. A polymer has been obtained (Japanese Patent Laid-Open No. 11-255829). Oka et al. Polymerized a fluorine-containing methacrylate having a perfluoroalkyl group in the side chain in the presence of an excess amount of alkylaluminum using an anionic polymerization initiator to produce a fluorine-containing polymer having high syndiotacticity. (Japanese Patent Laid-Open No. 2000-026539). Katsukawa et al. Obtained a fluorine-containing polymer having a high syndiotacticity by polymerizing a fluorine-containing methacrylate having a C 3-7 perfluoroalkyl group using an anionic polymerization initiator. No. 2011-225837). However, among these, although it is described that high syndiotacticity is superior in water and oil repellency, there is no description regarding the effect of high isotacticity on water and oil repellency.

Japanese Patent Laid-Open No. 11-255829 JP 2000-026539 A JP 2011-225837 A

EPA OPPT FACT SHEET April 14, 2003 (http://www.epa.gov/-opptintr/pfoa/pfoafacts.pdf) EPA Report "PRELIMINARY RISK ASSESSMENT OF THE DEVELOPMENTAL TOXICITY ASSOCIATED WITH EXPOSURE TO PERFLUORO-OCTANOIC ACID AND ITS SALTS" (http://www.epa.gov/opptintr/pfoa/pfoara.pdf)

  An object of the present invention is to provide a polymer having high isotacticity that exhibits high water and oil repellency and antifouling properties.

The polymer provided by the present invention is:
General formula (1):
CH ₂ = CH-COO-X-Rf (1)
(Wherein X represents a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms or a cyclic aliphatic hydrocarbon group, and Rf represents 1 carbon atom) Represents a linear or branched perfluoroalkyl group of ˜6), or the general formula (2):
CH ₂ = C (CH ₃ ) -COO-R (2)
(Wherein R represents a linear or branched aliphatic hydrocarbon group having 10 to 30 carbon atoms), and a polymer having a repeating unit derived from a monomer represented by: It is a polymer having an isotacticity of 65% or more of stereoregularity of the main chain of the repeating unit, and exhibits excellent water repellency, oil repellency and antifouling properties.

  The present invention provides an acrylic acid ester polymer having high isotacticity that exhibits excellent water and oil repellency and antifouling properties, and a method for producing the above polymer using an anionic polymerization initiator-containing catalyst.

  The polymer provided by the present invention is a polymer having high isotacticity, and has excellent water repellency, oil repellency and antifouling property.

The polymer of the present invention is:
A fluorine-containing polymer containing (or consisting of) the monomer of the general formula (1),
A fluoropolymer containing (or consisting of) the monomer of general formula (1) and the monomer of general formula (2), or containing (or consisting of) the monomer of general formula (2) It is a non-fluorine polymer.
In the fluoropolymer containing the monomer of the general formula (1) and the monomer of the general formula (2), the weight ratio of the monomer of the general formula (1) and the monomer of the general formula (2) is 1: 99-99: 1, such as 10: 90-90: 10.

The polymer provided by the present invention is:
General formula (1):
CH ₂ = CH-COO-X-Rf (1)
(In the formula, X represents a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms or a cyclic aliphatic hydrocarbon group, and Rf represents 1 carbon atom. Represents a linear or branched perfluoroalkyl group of ˜6), or a monomer represented by the general formula (2):
CH ₂ = C (CH ₃ ) -COO-R (2)
(Wherein R represents a linear or branched aliphatic hydrocarbon group having 10 to 30 carbon atoms), and a polymer having a repeating unit derived from a monomer represented by: The stereoregularity of the main chain of the repeating unit may have a high isotacticity of 65% or more, for example, 75% to 99.9%, especially 85% to 95% or 90% to 99%.

  The high isotacticity of the polymer of the present invention is important in the sense of compensating for a decrease in water and oil repellency associated with a decrease in the number of carbon atoms in the Rf group to 8 or less, such as 7 or less, particularly 6 or less. It is a special feature point. When comparing polymers having Rf groups or R groups having the same carbon number, the higher the isotacticity, the more the crystallization of the side chain Rf group or side chain R group of the polymer is induced. By suppressing the mobility of the Rf group or R group aligned with the surface to be measured, the receding contact angle exhibits a high value in the dynamic contact angle measurement, and the water repellency or oil repellency can be improved. In fact, the fact that the polymer of the present invention exhibits good water repellency or oil repellency is as disclosed in the examples described later, and its cause is derived from high isotacticity.

The perfluoroalkyl group represented by Rf in the general formula (1) may have 1 to 6 carbon atoms, and preferably 4 or 6. In particular, with respect to the water / oil repellency of a fluoropolymer derived from a monomer having an Rf group, the better the water / oil repellency of Rf, the better the water / oil repellency. More preferred.
The linear or branched aliphatic hydrocarbon group represented by R in the general formula (2) may have 10 to 30 carbon atoms, and preferably 16 to 30 carbon atoms. In particular, with respect to the water repellency of a polymer having a repeating unit derived from a monomer having an R group, the better the water repellency is obtained as the carbon number of the R group is larger, and the side chain R group crystals In view of ease of conversion and industrial production, a linear aliphatic hydrocarbon group having 18 to 22 carbon atoms is more preferable. Examples of the aliphatic hydrocarbon group are saturated or unsaturated aliphatic hydrocarbon groups such as an alkyl group, a cycloalkyl group, and an alkylene group.

  X in the general formula (1) represents a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a cyclic aliphatic hydrocarbon group. For example, a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms is linear or branched such as a methylene group, an ethylene group, a trimethylene group, a 2-methylethylene group, a styryl group, a hexylene group, and an octylene group. -Like alkylene group. Examples of the divalent aromatic hydrocarbon group having 6 to 10 carbon atoms include a 1,4-phenylene group, a 1,4-bismethylenephenylene group, and a 1,4-bisethylenephenylene group. Examples of the cyclic aliphatic hydrocarbon group having 6 to 10 carbon atoms include 1,4-cyclohexylene group, 1,4-bismethylenecyclohexylene group, and 1,4-bisethylenecyclohexylene group.

The monomer of the general formula (1) of the present invention is preferably the general formula (3):
CH ₂ = CH-COO- (CH ₂ ) _m- (CF ₂ ) _n -F (3)
(Wherein m is 1 to 10 and n is 1 to 6). Specific examples of the monomer of the general formula (3) include
CH ₂ = CH-COO-CH _2- (CF ₂ ) ₂ F,
CH ₂ = CH-COO-CH _2- (CF ₂ ) ₄ F,
CH ₂ = CH-COO-CH _2- (CF ₂ ) ₆ F,
CH ₂ = CH-COO- (CH ₂ ) _2- (CF ₂ ) ₂ F,
CH ₂ = CH-COO- (CH ₂ ) _2- (CF ₂ ) ₄ F,
CH ₂ = CH-COO- (CH ₂ ) _2- (CF ₂ ) ₆ F,
Etc. Of these, preferably
CH ₂ = CH-COO-CH _2- (CF ₂ ) ₆ F,
CH ₂ = CH-COO- (CH ₂ ) _2- (CF ₂ ) ₆ F,
Etc. are used.

The monomer of the general formula (2) of the present invention is preferably the general formula (4):
CH ₂ = C (CH ₃ ) -COO- (CH ₂ ) _y -H (4)
(Wherein y represents 10 to 30). y may for example be 12 to 26, in particular 14 to 24. Specific examples of the monomer represented by the general formula (4) include decyl methacrylate, dodecyl methacrylate, tridecyl methacrylate, tetradecyl methacrylate, cetyl methacrylate, stearyl methacrylate, and behenyl methacrylate. Of these, stearyl methacrylate and behenyl methacrylate are preferably used.

  The crystallinity of the polymer of the present invention increases with an increase in isotacticity. As the crystallinity increases, the water and oil repellency can be improved. Even if it is a copolymer of the monomer of the general formula (1) or (2) and another monomer that can be copolymerized therewith, the isotactic structure of the main chain of the repeating unit of the monomer of the present invention The water and oil repellency improves as the city increases.

  The present invention provides a method for producing a polymer having high isotacticity by using an anionic polymerization initiator, for example, an anionic polymerization initiator-containing catalyst. As the anionic polymerization initiator, at least one first organometallic compound selected from the group consisting of an organic lithium compound, an organic potassium compound, and a Grignard reagent can be used. The first organometallic compound is preferably an organolithium compound.

  The catalyst of the present invention may contain a second organometallic compound of at least one metal selected from metals belonging to Group 1 of the periodic table, in addition to the first organometallic compound (anionic polymerization initiator).

As the first organometallic compound, a known anionic initiator having an alkali metal or alkaline earth metal as a counter cation can be used. For example, n-PrLi, i-PrLi, n-BuLi, sec-BuLi, t-BuLi, or an alkyl lithium compound such as t-AmLi, (CH ₃ ) ₂ C (Li) COOCH ₃ , (CH ₃ ) ₂ C (Li) COOC ₂ H ₅ , (CH ₃ ) ₂ C (Li) COO (CH ₂ ) ₂ CH ₃ , (CH ₃ ) ₂ C (Li) COOCH (CH ₃ ) ₂ (hereinafter Li-i- (Represented as PrIB), α-lithioisobutyric acid ester compounds such as (CH ₃ ) ₂ C (Li) COOC (CH ₃ ) ₃ , n-Pr-MgBr, i-Pr-MgBr, n-Bu-MgBr, sec- Examples thereof include Grignard compounds such as Bu-MgBr, t-Bu-MgBr, and t-Am-MgBr. Of these, preferably i-PrLi, Li-i-PrIB, sec-BuLi, t-BuLi, t-AmLi, i-Pr-MgBr, sec-Bu-MgBr, t-Bu-MgBr and t-Am -MgBr may be used, particularly preferably t-BuLi and Li-i-PrIB may be used.

As a 2nd organometallic compound used by this invention, the organometallic compound containing the metal which belongs to a well-known periodic table group 1 can be mentioned. Examples thereof include lithium silanolates such as Me ₃ SiOLi, t-BuMe ₂ SiOLi and Et ₃ SiOLi, and metal alkoxides such as t-BuOLi and t-BuOK.
The amount of the first organometallic compound may be 0.1 to 10 mol%, for example 0.5 to 5 mol%, based on the monomer, and the amount of the second organometallic compound may be the first organometallic compound. It may be 1 molar equivalent or more, for example, 1 to 50 molar equivalents.

  The polymerization method may be a batch charging method, a split charging method or a continuous charging method. In particular, when two or more monomers are copolymerized, it is preferable in that a block copolymer having a homogeneous composition can be obtained by dividing or continuously charging any one or more monomers. .

The molecular weight of the polymer of the present invention is 2,000 to 1,000,000, preferably 3,000 to 500,000, and more preferably 4,000 to 300,000 in terms of number average molecular weight (Mn). The number average molecular weight is calculated by calculating the ratio of the monomer unit to the terminal group in the polymer from the signal intensity derived from the start terminal and the signal intensity derived from the polymer main chain or side chain by ¹ H-NMR measurement. Asked.

The molecular weight distribution of the fluoropolymer of the present invention may be 2.5 or less, specifically 2.0 or less, preferably 1.5 or less, for example, 1.3 or less. You can do it.
The crystallinity of the polymer was evaluated by the number of sharp diffraction line peaks in the X-ray diffraction measurement derived from the crystal part of the polymer, and the crystal melting point and melting enthalpy values in the thermal property measurement. That is, a large number of diffraction line peaks and a high crystal melting point and melting enthalpy value indicate high crystallinity of the polymer.

When using a 1st organometallic compound and a 2nd organometallic compound as a catalyst, the use molar ratio of a 2nd organometallic compound is 1 mol or more with respect to 1 mol of anionic polymerization initiators (1st organometallic compound), Good. For example, Me ₃ SiOLi may be 1 mol or more with respect to 1 mol of Li-iPrIB.

In the polymerization reaction, it is preferable to use a solvent in which the monomer and the resulting polymer are dissolved and which does not freeze even at a low polymerization reaction temperature. As the solvent, for example, a fluorine-containing solvent alone, a non-fluorine solvent alone, or a mixed solvent of a fluorine-containing solvent and a non-fluorine solvent may be used. Preferred examples of the fluorine-containing solvent include CFC-316 (C ₄ Cl ₄ F ₆ ), CFC-519 (C ₆ Cl ₅ F ₉ ), HFC-134a (1,1,1,2-tetrafluoroethane), Fluorine-containing aliphatics such as HCFC-225 (C ₃ HCl ₂ F ₅ ), Solcan 365 mfc (C ₄ H ₅ F ₅ ), Vertrel XF (C ₅ H ₂ F ₁₀ ), Zeolora H (C ₅ H ₃ F ₇ ) Compounds, perfluorobenzene, fluorine-containing aromatic compounds such as α, α, α-trifluoromethylbenzene, 1,3-bis (trifluoromethyl) benzene (m-XHF), perfluorobutyl methyl ether, perfluorobenzene Fluorine-containing ether compounds such as fluorobutyl ethyl ether are exemplified. Non-fluorinated solvents include hydrocarbon ethers such as toluene, xylene aromatic compounds, diethyl ether, butyl methyl ether, dibutyl ether, tetrahydrofuran (THF), 1,4-dioxane, monoglyme, diglyme, triglyme, and tetraglyme. And chlorinated aliphatic compounds such as methylene chloride, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane. When preparing a fluorinated polymer, the solvent preferably contains a fluorinated solvent from the viewpoint of good polymerization reaction and high isotacticity. Since isotacticity is high, m-XHF or HCFC-225 single solvent, m-XHF and HCFC-225 mixed solvent, m-XHF and / or HCFC-225 mixed with toluene and / or methylene chloride A solvent is preferred. The amount of the solvent may be 1 to 10000 parts by weight, for example 10 to 1000 parts by weight with respect to 100 parts by weight of the monomer.

  The polymerization reaction temperature is a temperature at which the solvent does not freeze, and is usually 0 ° C. or lower, for example, in the range of −80 ° C. to 0 ° C.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these Examples.
In the following, parts or% represents parts by weight or% by weight unless otherwise specified.

  Analysis of the polymer and measurement of water and oil repellency were performed as follows.

"Number average molecular weight"
The number average molecular weight (Mn) of the fluoropolymer was measured by ¹ H-NMR (Varian Unity INOVA500) at 500 MHz or ¹ H-NMR (JEOL ECS-400) at 400 MHz, C6F6 / C6D6 = 95/5. It carried out at 70 degreeC in the mixed solvent. Signal intensity around 4.2 ppm of methine group of i-Pr group of polymerization initiator and signal intensity around 1.7 to 2.6 ppm derived from main chain CH ₂ group, or ester CH ₂ group present in side chain From the signal intensity in the vicinity of 4.5 to 4.7 ppm derived from the above, the ratio of the monomer unit to the terminal group in the polymer was calculated. On the other hand, the number average molecular weight (Mn) of the non-fluorinated polymer was measured using Shodex GPC-104 (column LF604 × 2 series) manufactured by SHOWA DENKO using tetrahydrofuran as a solvent. The chromatogram was calibrated using a standard polystyrene sample.

`` Stereoregularity ''
The stereoregularity analysis of the polyacrylate followed the analysis method of polymethyl acrylate by Matsuzaki et al. (J. Polym. Sci., A-1, 5, 2167 (1967)). That is, in ¹ H-NMR, three absorptions based on main chain methylene protons appearing in the vicinity of 2 ppm were used, and isotactic dyad (m) was determined from the absorption of low and high magnetic fields. On the other hand, the analytical method of stereoregularity of polymethacrylate is established by Nishioka (J. Polym. Sci., 45, 232 (1960), and Bovey (J. Polym. Sci., 44, 173 (1960). Therefore, the stereoregularity of the polymer follows that method: In ¹ H-NMR, three absorptions based on α-methyl group protons appearing in the vicinity of 1 ppm are utilized, and the isotacticity is less than that of low magnetic field absorption. The tactic triad (mm) was determined.

"Thermal characteristics"
The glass transition temperature (Tg), crystal melting point (Tm) and melting enthalpy (ΔH) of the polymer were measured with a thermal analyzer DSC (SEIKO-RDC220) in a temperature range of −50 to 150 ° C. Measured in minutes.

"Static contact angle"
The static contact angle, which is one of the evaluations of the water / oil repellency of the polymer, was measured as follows. The water repellency was determined by measuring the static contact angle of water droplets (surface tension γi = 72 mN / m), and the oil repellency was determined by measuring the static contact angle of n-hexadecane droplets (surface tension γi = 27 mN / m). That is, the fluorinated polymer is HCFC-225 or HFE7300 (1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-trifluoromethyl-pentane), or A non-fluorine polymer is made into a 1 wt% solution in a toluene solvent, applied to a glass substrate by a spin coating method (2000 rpm), and when HCFC-225 is used, it is heat-treated at 75 ° C. for 3 minutes to produce HFE-7300 or toluene. Was used, it was dried at room temperature for 48 hours to form a film. Next, the contact angle was measured with a contact angle meter (trade name “CA-VP”) manufactured by Kyowa Interface Science Co., Ltd. The measurement environment was set to a temperature of 15 to 20 ° C. and a relative humidity of 50 to 70% in accordance with JIS R3257. The larger the contact angle, the better the water and oil repellency.

"Dynamic contact angle and sliding angle"
The dynamic contact angle, which is one of the evaluations of the water and oil repellency of the polymer, was measured as follows. Water repellency was determined by measuring the dynamic contact angle of water droplets (surface tension γi = 72 mN / m), and oil repellency was determined by measuring the dynamic contact angle of n-hexadecane droplets (surface tension γi = 27 mN / m). The details of the dynamic contact angle were obtained by measuring the advancing contact angle: θa (deg), the receding contact angle: θr (deg), and the falling angle: α (deg). That is, a polymer film was formed on a glass substrate by the same method as described above, and the contact angle was measured with a contact angle meter (trade name “CA-VP”) manufactured by Kyowa Interface Science Co., Ltd. as described above. The measurement environment was set to a temperature of 15 to 20 ° C. and a relative humidity of 50 to 70% in accordance with JIS R3257. The smaller the hysteresis representing the difference between θa and θr and the smaller the falling angle, the better the water / oil repellency.

Initiator Synthesis Example: Synthesis of α-Lithioisobutyric Acid Lochmann L. The synthesis was performed according to the literature (J. Organomet. Chem. 1973, 50, 9.). 12.5 mL of a hexane solution containing 20 mmol of n-butyllithium in 2.80 mL (20 mmol) of diisopropylamine was added at 0 ° C. under dry nitrogen and kept at 0 ° C. for 1.5 hours. To this, 25.6 mL (20 mmol) of isopropyl isobutyrate was added at room temperature, kept for 1 hour, and then concentrated under reduced pressure. Recrystallize with heptane and use the corresponding lithium enolate (Li-iP
2.3 g (yield 85%) of white crystals of rIB) were obtained.

Example 1
1,3-bis (trifluoromethyl) benzene (m-XHF) 10 mL, fluorine-containing monomer 2- (perfluorohexyl) ethyl acrylate CH ₂ = CH-COO- (CH ₂ ) _2- (CF ₂ ) ₆ 4.18 g (10 mmol) of F (hereinafter abbreviated as “C6-SFA”) was placed in a glass ampoule and kept at −40 ° C. under nitrogen. Next, 0.424 mL of a benzene solution containing 0.2 mmol of lithium enolate (Li-i-PrIB) was added and sealed, and the polymerization reaction was carried out by keeping the temperature at −40 ° C. for 24 hours. After the reaction was completed, a small amount of hydrochloric acid methanol was added to stop the polymerization reaction, and the reaction solution was poured into a large amount of methanol to precipitate a polymer. The resulting precipitate was collected by filtration, washed, and then vacuum dried to obtain the fluoropolymer of the present invention. Table 1 shows the obtained polymerization results and product analysis results.

Example 2
10 mL of m-XHF, 0.245 mL of a benzene solution containing 0.2 mmol of Li-i-PrIB, and 0.237 mL of a toluene solution containing 0.2 mmol of lithium trimethylsilanolate (Me3SiOLi) were placed in a glass ampule and −40 under nitrogen. Kept at ℃. Next, 4.18 g (10 mmol) of C6-SFA was added and sealed, and the polymerization reaction was carried out at -40 ° C. for 24 hours. The polymerization reaction was stopped and the subsequent procedure was carried out in the same manner as in Example 1 to obtain the fluoropolymer of the present invention. Table 1 shows the obtained polymerization results and product analysis results.

Example 3
A procedure similar to that in Example 2 was used, except that HCFC-22510 mL and 5 mmol of lithium trimethylsilanolate (Me ₃ SiOLi) were used in place of 10 mL of m-XHF and polymerization was performed at −78 ° C. Table 1 shows the obtained polymerization results and product analysis results.

Example 4
Polymerization was carried out at −78 ° C. for 72 hours using 7 mL of m-XHF, 3 mL of toluene, and 0.6 mmol of ethylaluminum bis-2,6-di-tert-butylphenoxide (EtAl (ODBP) ₂ ) instead of 10 mL of m-XHF. Except for this, the same procedure as in Example 2 was used. Table 1 shows the obtained polymerization results and product analysis results.

Comparative Example 1 (Fluoropolymer from "C8-SFA" monomer by radical polymerization)
2- (perfluorooctyl) ethyl acrylate CH ₂ = CH—COO— (CH ₂ ) ₂ — (CF ₂ ) ₈ F (hereinafter abbreviated as “C8-SFA”) instead of fluorine-containing monomer C6-SFA 5.18 g (10 mmol) is used, and 32.8 mg (0.2 mmol) of azobisisobutyronitrile (AIBN) is used instead of Li-i-PrIB, and the polymerization temperature is 60 ° C. Except for this, the same procedure as in Example 1 was repeated to obtain a fluoropolymer. Table 1 shows the obtained polymerization results and product analysis results.

Comparative Example 2 (Fluoropolymer from "C6-SFA" monomer by radical polymerization)
The same procedure as in Example 1 was repeated except that 32.8 mg (0.2 mmol) of azobisisobutyronitrile (AIBN) was used instead of Li-i-PrIB, and the polymerization temperature was 60 ° C. A fluoropolymer was obtained. Table 1 shows the obtained polymerization results and product analysis results.

（表中、含フッ素単量体；CH₂=CHCOO-(CH₂)₂-(CF₂)_n-F、ｎ＝６：Ｃ６−ＳＦＡ、ｎ＝８：Ｃ８−ＳＦＡ。 ｍ；イソタクチックダイアド。 n. d.: 観測されず。）

(In the table, a fluorine-containing _{monomer; CH 2 = CHCOO- (CH 2} ) 2 - (CF 2) n -F, n = 6: C6-SFA, n = 8:. C8-SFA m; isotactic Dyado nd: not observed.)

  From Table 1, it can be seen that the fluoropolymer according to the present invention can adjust the isotacticity arbitrarily as compared with the polymer obtained by radical polymerization, and has a clear Tm at high isotacticity. However, the higher the isotacticity, the greater the melting enthalpy. This suggests that isotacticity is derived and crystallinity of the fluoropolymer is induced.

"Measurement of crystallinity (X-ray diffraction)"
The powder X-ray diffraction pattern of the fluoropolymer obtained in Example 1 and Comparative Example 2 was reflected by a reflection method using a monochromatic CuKα radiation source at 40 kV and 50 mA using RAD-rA type manufactured by Rigaku Corporation. It was measured. The obtained results are shown in Table 2.

（表中、n. d.: 観測されず。）

(In the table, nd: not observed.)

  From Table 2, in the low isotacticity fluoropolymer obtained by radical polymerization of Comparative Example 2, only the diffraction line attributed to the packing between perfluoroalkyl groups in the molecule around 2θ = 18 deg. In comparison with the observed, the fluoropolymer having high isotacticity of the present invention is attributed to a lamellar structure in the vicinity of 2θ = 4 deg, 7 deg, and 10 deg in addition to the diffraction line in the vicinity of 2θ = 18 deg. A diffraction line is also observed, indicating that the fluoropolymer of the present invention has high crystallinity.

Example 5
0.353 mL of a benzene solution containing 0.2 mmol of lithium enolate (Li-i-PrIB), 4.63 mL of a toluene solution containing 5 mmol of lithium trimethylsilanolate (Me ₃ SiOLi), and 20 mL of toluene are placed in a glass ampoule, and nitrogen is added. Maintained at 0 ° C. below. Next, 3.39 g (10 mmol) of monomeric stearyl methacrylate CH ₂ ═C (CH ₃ ) —COO— (CH ₂ ) 18 H (hereinafter abbreviated as “StMA”) was added and sealed, and the mixture was sealed at 0 ° C. The polymerization reaction was carried out for 24 hours. After the reaction was completed, a small amount of hydrochloric acid methanol was added to stop the polymerization reaction, and the reaction solution was poured into a large amount of methanol to precipitate a polymer. The resulting precipitate was collected by filtration, washed and then vacuum dried to obtain the polymer of the present invention. Table 3 shows the obtained polymerization results and the analysis results of the products.

Comparative Example 3 (Non-Fluoropolymer from “StMA” Monomer by Radical Polymerization)
The same procedure as in Example 5 was repeated except that 32.8 mg (0.2 mmol) of azobisisobutyronitrile (AIBN) was used instead of Li-i-PrIB, and the polymerization temperature was 60 ° C. A non-fluorinated polymer was obtained. Table 3 shows the obtained polymerization results and the analysis results of the products.

（表中、非フッ素単量体ＳｔＭＡ：CH₂=C(CH₃)COO-(CH₂)₁₈-H。 ｍｍ：イソタクチックトリアド。）
表２から、本発明の重合体は、ラジカル重合で得られた重合体と比較して、高いイソタクチシチィーであり、且つ、Ｔｍが高くなっている。これは、イソタクチシチィーが由来して重合体の結晶性が誘起したことを示唆している。

(In the table, fluorine-free monomer _{StMA: CH 2 = C (CH} 3) COO- (CH 2) 18 -H mm:. Isotactic triad.)
From Table 2, the polymer of this invention is high isotacticity compared with the polymer obtained by radical polymerization, and Tm is high. This suggests that isotacticity is derived and the crystallinity of the polymer is induced.

Example 6
The fluoropolymer obtained in Example 1 was made into 5 mL of a 1% solution in a HFE-7300 solvent, applied to a glass substrate by a spin coating method (2000 rpm), and then dried at room temperature for 48 hours to form a film. Table 4 shows the measurement results of the static contact angle and dynamic contact angle with respect to water of this coating film, and Table 5 shows the measurement result of the static contact angle and dynamic contact angle with respect to n-hexadecane.

Example 7
A film was formed by repeating the same procedure as in Example 6 except that the fluoropolymer obtained in Example 2 was used instead of the fluoropolymer obtained in Example 1. Table 4 shows the measurement results of the static contact angle and dynamic contact angle with respect to water of this coating film, and Table 5 shows the measurement result of the static contact angle and dynamic contact angle with respect to n-hexadecane.

Example 8
A film was formed by repeating the same procedure as in Example 6 except that the fluoropolymer obtained in Example 3 was used instead of the fluoropolymer obtained in Example 1. Table 4 shows the measurement results of the static contact angle and dynamic contact angle with respect to water of this coating film, and Table 5 shows the measurement result of the static contact angle and dynamic contact angle with respect to n-hexadecane.

Example 9
A film was formed by repeating the same procedure as in Example 6 except that the fluoropolymer obtained in Example 4 was used instead of the fluoropolymer obtained in Example 1. Table 4 shows the measurement results of the static contact angle and dynamic contact angle with respect to water of this coating film, and Table 5 shows the measurement result of the static contact angle and dynamic contact angle with respect to n-hexadecane.

Comparative Example 4
The fluoropolymer obtained in Comparative Example 1 was made into 5 mL of a 1% solution in a HCFC-225 solvent, applied to a glass substrate by a spin coating method (2000 rpm), and then heat-treated at 75 ° C. for 3 minutes to form a film. Table 4 shows the measurement results of the static contact angle and dynamic contact angle with respect to water of this coating film, and Table 5 shows the measurement result of the static contact angle and dynamic contact angle with respect to n-hexadecane.

Comparative Example 5
A film was formed by repeating the same procedure as in Example 7 except that the fluoropolymer obtained in Comparative Example 2 was used instead of the fluoropolymer obtained in Example 1. Table 4 shows the measurement results of the static contact angle and dynamic contact angle with respect to water of this coating film, and Table 5 shows the measurement result of the static contact angle and dynamic contact angle with respect to n-hexadecane.

（表中、ｍ：イソタクチックダイアド。＞９０：ガラス基板を９０ｄｅｇに傾斜しても水滴が転落しなかったことを表す。ｎ．ｄ．：転落角が＞９０であったため評価できなかったことを表す。）
表４から、本発明の含フッ素重合体は、イソタクチシチィーが高くなるほど、水に対する転落角およびヒステリシスが低下する。即ち、高いイソタクチシチィーを有する本発明の含フッ素重合体は撥水性が優れていることが判る。

(In the table, m: isotactic dyad.> 90: Indicates that the water droplet did not fall even when the glass substrate was tilted to 90 deg.) Nd: Could not be evaluated because the fall angle was> 90. Represents this.)
From Table 4, the fluorinated polymer of the present invention has lower drop angle and hysteresis with respect to water as the isotacticity becomes higher. That is, it can be seen that the fluoropolymer of the present invention having high isotacticity is excellent in water repellency.

（表中、ｍ：イソタクチックダイアド。＞９０：ガラス基板を９０ｄｅｇに傾斜しても水滴が転落しなかったことを表す。ｎ．ｄ．：転落角が＞９０であったため評価できなかったことを表す。）
表５から、本発明の含フッ素重合体は、イソタクチシチィーが高くなるほど、油（ｎ−ヘキサデカン）に対する転落角およびヒステリシスが低下する。即ち、高いイソタクチシチィーを有する本発明の含フッ素重合体は撥油性が優れていることが判る。

(In the table, m: isotactic dyad.> 90: Indicates that the water droplet did not fall even when the glass substrate was tilted to 90 deg.) Nd: Could not be evaluated because the fall angle was> 90. Represents this.)
From Table 5, as the isotacticity of the fluoropolymer of the present invention increases, the falling angle and hysteresis with respect to oil (n-hexadecane) decrease. That is, it can be seen that the fluoropolymer of the present invention having high isotacticity is excellent in oil repellency.

Example 10
The polymer obtained in Example 5 was made into 5 mL of a 1% solution in a toluene solvent, applied to a glass substrate by a spin coating method (2000 rpm), and then dried at room temperature for 48 hours to form a film. Table 6 shows the measurement results of the static contact angle and dynamic contact angle of this coating film with respect to water.
Comparative Example 6
A film was formed by repeating the same procedure as in Example 10 except that the polymer obtained in Comparative Example 3 was used instead of the polymer obtained in Example 5. Table 6 shows the measurement results of the static contact angle and dynamic contact angle of this coating film with respect to water.

（表中、ｍｍ：イソタクチックトリアド。）
表６から、本発明の重合体は、イソタクチシチィーが高くなるほど、水に対する転落角およびヒステリシスが低下する。即ち、高いイソタクチシチィーを有する本発明の重合体は撥水性が優れていることが判る。

(In the table, mm: isotactic triad.)
From Table 6, as for the polymer of this invention, the fall angle with respect to water and hysteresis fall, so that isotacticity becomes high. That is, it can be seen that the polymer of the present invention having high isotacticity is excellent in water repellency.

  The polymer provided by the present invention is an environment-friendly polymer having a perfluoroalkyl group having 1 to 6 carbon atoms or an aliphatic hydrocarbon group having 10 to 30 carbon atoms in the side chain and having high isotacticity. Since it is a coalescence and has excellent water repellency or oil repellency, it can be widely used as a surface treatment agent for paper, fiber, plastic, metal and the like, for example, a water repellant, an oil repellant, and an antifouling agent.

Claims (11)

General formula (1):
CH ₂ = CH-COO-X-Rf (1)
(In the formula, X represents a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms or a cyclic aliphatic hydrocarbon group, and Rf represents 1 carbon atom. Represents a linear or branched perfluoroalkyl group of ˜6), or a monomer represented by the general formula (2):
CH ₂ = C (CH ₃ ) -COO-R (2)
(Wherein R represents a linear or branched aliphatic hydrocarbon group having 10 to 30 carbon atoms), and a polymer having a repeating unit derived from a monomer represented by: A polymer having isotacticity in which the stereoregularity of the main chain of the repeating unit is 65% or more. The monomer of general formula (1) is represented by general formula (3):
CH ₂ = CH-COO- (CH ₂ ) _m- (CF ₂ ) _n -F (3)
The polymer of Claim 1 which is a monomer represented by (In formula, m is 1-10 and n is 1-6.). The monomer of general formula (2) is represented by general formula (4):
CH ₂ = C (CH ₃ ) -COO- (CH ₂ ) _y -H (4)
The polymer according to claim 1, wherein y is a monomer represented by the formula:   The method for producing a polymer according to any one of claims 1 to 3, wherein a polymerization reaction is performed using an anionic polymerization initiator.   The production method according to claim 4, wherein the anionic polymerization initiator is at least one first organometallic compound selected from the group consisting of an organolithium compound, an organopotassium compound, and a Grignard reagent.   The production method according to claim 5, wherein the first organometallic compound is an organolithium compound.   The catalyst according to any one of claims 4 to 6, comprising a second organometallic compound of at least one metal selected from metals belonging to Group 1 of the periodic table in addition to the first organometallic compound. The manufacturing method as described in.   The production method according to claim 7, wherein the second organometallic compound is at least one organometallic compound selected from organolithium compounds.   The production method according to claim 7 or 8, wherein the second organometallic compound is an organolithium compound.   A surface treatment agent in which the polymer according to any one of claims 1 to 3 is dispersed in an organic solvent or water.   The surface treating agent according to claim 10, which is at least one of a water repellent, an oil repellent and an antifouling agent.