JPH08217872A - Star type block polymer, its production, ionic conductor and lithium cell using the same - Google Patents

Abstract

PURPOSE: To obtain the subject polymer useful as a material for cells, a surfactant, etc., by adding ethylene oxide to a polyhydric alcohol, forming an adduct and successively adding and reacting trifluoropropylene oxide with the resultant adduct in the presence of an alkali metallic hydroxide. CONSTITUTION: This polymer of formula II [R<1> is a 1-16C (substituted) aliphatic hydrocarbon, R<2> is H, a 1-16C (substituted) alkyl, alkenyl, F-substituted alkyl, (alkyl-substituted)phenyl or (meth)acryloyl; m and n are each 1 or more; L is 3-8]. The polymer is obtained by adding and reacting trifluoropropylene oxide of formula I with an adduct, having ethylene oxide block units and prepared by adding and reacting ethylene oxide with a polyhydric alcohol having 3-8 hydroxyl groups is the presence of an alkali metallic hydroxide (e.g. NaOH), forming trifluoropropylene oxide block units and then terminating the reaction.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel fluorine-containing block polymer having three or more block polyether chains and useful as a battery material or a surfactant.

[0002]

2. Description of the Related Art Poly (trifluoropropylene oxide) is a polyether having a chemically stable trifluoromethyl group and exhibits special properties such as water repellency, low solvent solubility and low refractive index. It is useful as an intermediate in rubber production. On the other hand, ethylene oxide polymers are useful as surfactants and raw materials for cosmetics.

The block copolymer having each polymerized unit of both polymers (hereinafter, trifluoropropylene oxide block unit is A and ethylene oxide block unit is B) in the molecule has both characteristics. It is an interesting copolymer because the content of CF ₃ groups can be adjusted according to the application. Such block copolymers have already been disclosed in JP-A-5-310909,
It is proposed in Japanese Patent Laid-Open No. 6-145338.

[0004]

However, the above-mentioned known block copolymer is a so-called AB type or ABA type.
Is a linear polymer structure of the mold.

Therefore, an object of the present invention is to provide a star-shaped block polymer having more stericity.

[0006]

Means for Solving the Problems As a result of intensive studies, the present inventor has invented the following star block polymers.

That is, the present invention provides (1) a star block polymer represented by the following formula (1):

[0008]

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(Wherein R ¹ is an optionally substituted aliphatic hydrocarbon residue having 1 to 16 carbon atoms, R ² is hydrogen, an optionally substituted alkyl group having 1 to 16 carbon atoms, alkenyl Group, fluorine-substituted alkyl group, fluorine-substituted alkenyl group, phenyl group, alkyl-substituted phenyl group, acryloyl group, methacryloyl group, m ≧ 1, n ≧ 1, L =
(2) An integer of 3 to 8) (2) The star block polymer according to (1) above, wherein R ² in the formula (1) is an acryloyl group or a methacryloyl group, and (3) a polymer having 3 to 8 hydroxyl groups. To an adduct having an ethylene oxide block unit obtained by adding ethylene oxide to a polyhydric alcohol, a trifluoropropylene oxide represented by the following formula (2) is added in the presence of an alkali metal hydroxide to cause a reaction, and a trifluoropropylene oxide is further added. The method for producing a star block polymer as described in (1) above, wherein the reaction is stopped after forming the fluoropropylene oxide block unit.

[0010]

[Chemical 6]

(4) An ionic conductor characterized by containing an alkali metal salt in the star block polymer of the formula (1) described in (1), (5) the formula (1) described in (1) above. ) An ionic conductor characterized by containing an alkali metal salt and an organic solvent in the star block polymer, (6) comprising the crosslinked polymer of the star block polymer according to (2) above and an alkali metal salt. An ionic conductor characterized by that
(7) An ionic conductor comprising a cross-linked polymer of the star block polymer according to (2) above, an alkali metal salt and an organic solvent, (8) a star polyether represented by the following formula (3): An ionic conductor comprising an alkali metal salt and a cross-linked star-shaped block polymer as described in (2) above.

[0012]

[Chemical 7]

(Wherein R ³ is an optionally substituted aliphatic hydrocarbon residue having 1 to 16 carbon atoms, OEt is an ethylene oxide unit, OPr is a propylene oxide unit, Ac is an acryloyl group or methacryloyl group, p ≧ 1, q
≧ 0, r is an integer of 3 to 8) (9) A cross-linked star-shaped block polymer, an alkali metal salt, and a star-shaped block polymer as described in (2), wherein a star-shaped polyether represented by the following formula (3) is mixed. An ionic conductor characterized by comprising an organic solvent,

[0014]

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(Wherein R ³ is an optionally substituted aliphatic hydrocarbon residue having 1 to 16 carbon atoms, OEt is an ethylene oxide unit, OPr is a propylene oxide unit, Ac is an acryloyl group or a methacryloyl group, p is ≧ 1, q
≧ 0, r is an integer of 3 to 8) (10) The present invention relates to a lithium battery containing at least one or more of the ion conductors described in (4) to (9).

In the star-shaped block polymer represented by the formula (1) of the present invention, R ¹ is a residue of a polyhydric alcohol and is selected from an optionally substituted aliphatic hydrocarbon having 1 to 16 carbon atoms. . Examples of preferable R ¹ include hydrocarbon residues such as glycerin, pentaerythritol, trimethylolethane, dipentaerythritol, mannitol, D-sorbitol and tripentaerythritol. Further, these substituents are not particularly limited as long as they do not interfere with the reaction with ethylene oxide or trifluoropropylene oxide, and examples thereof include the same alkyl groups and alkenyl groups as those described below for R ^2. To be Further, m and n are ≧ 1.

In R ² , the alkyl or alkenyl group having 1 to 16 carbon atoms which may be substituted is methyl, ethyl, n-propyl, isopropyl or n.
-Butyl, tert-butyl, 1-pentyl, 3-methyl-1-butyl, 3-methyl-1-heptyl, 2-ethyl-1-hexyl, 1-hexyl, 1-heptyl, 1-
Octyl, 1-nonyl, 1-decyl, 1-undecyl,
1-dodecyl, 1-tridecyl, 1-tetradecyl, 1
Examples thereof include an alkyl group such as pentadecyl and an alkenyl group such as allyl and crotyl. Furthermore,
As these substituents, those containing fluorine may be used. Examples of the fluorine-substituted alkyl group and the fluorine-substituted alkenyl group include trifluoroethyl, perfluorobutyl, perfluoro-3-methylbutyl, 2,2,3,3-tetrafluoropropyl, 2- (perfluorohexyl) ethyl, 2- Fluorine-substituted alkyl groups such as (perfluoro-3-methylbutyl) ethyl and 6- (perfluorohexyl) hexyl, or 2,2,3,4,4-perfluoro-3-butenyl, 3-perfluorooctyl-2.
And fluorine-substituted alkenyl groups such as propenyl. Further, the phenyl group of R ² and the alkyl-substituted phenyl group include phenyl, 4-methylphenyl, 4-ethylphenyl, 4-isopropylphenyl, 4-propylphenyl, 4-sec-butylphenyl and 4-tert.
-Butylphenyl, 3,4-dimethylphenyl, 4-isopropyl-3-methylphenyl and the like can be mentioned. Further, as R ² , an acryloyl group and a methacryloyl group are also preferable. In the case of R ² acryloyl group and methacryloyl group, 1 ≦ m ≦ 200 and 1 ≦ n ≦ 100 are preferable. When m and n exceed this value, the amount of terminal functional groups decreases and the crosslinking density decreases, so the mechanical strength of the film becomes weak.

Examples of the polyhydric alcohol having 3 to 8 hydroxyl groups used in the method for producing the star block polymer of the present invention include, for example, glycerin, pentaerythritol, trimethylolethane, dipentaerythritol, mannitol, D-sorbitol, tri- and tri-. Examples thereof include pentaerythritol.

Examples of the alkali metal hydroxide used in the present invention include sodium hydroxide and potassium hydroxide.

The star block polymer of the present invention can be manufactured as follows. First, ethylene oxide is added to a polyhydric alcohol having 3 to 8 hydroxyl groups in the presence of an alkali metal hydroxide to form an ethylene oxide block unit at each hydroxyl group. Then
Trifluoropropylene oxide is added to the reaction system, and if necessary, an alkali metal hydroxide is further added, and trifluoropropylene oxide is added to the ethylene oxide block unit to form a trifluoropropylene oxide block unit. The above two reaction steps are
It may be carried out continuously or separately. That is, it is also possible to preliminarily produce an intermediate obtained by adding an ethylene oxide unit to a polyhydric alcohol by the reaction of the first step, and use this as a starting material to carry out the reaction of the second step.

The amount of the alkali metal hydroxide used is such that in the reaction for forming ethylene oxide block units, the amount is 1/1000 to 2 times the molar amount of the alcohol group, particularly 1/10.
The molar amount is preferably 0 to 1/2 times, and can be appropriately selected according to the target molecular weight. Also, in the reaction that forms the trifluoropropylene oxide block unit,
A molar amount of 1/10 to 10 times, particularly 0.9 to 1.2 times the molar amount of the alcohol group is preferable.

The above reaction can be carried out either in the presence of a solvent or without a solvent, but it is preferred to use a solvent in the reaction for forming the trifluoropropylene oxide block unit. Examples of such a solvent include 1,2-dimethoxyethane, dioxane, THF,
Examples thereof include diethylene glycol dimethyl ether.

The polymerization temperature for the reaction to form ethylene oxide block units is 40 to 200 ° C, especially 80 to 150 ° C.
Is preferred, and the polymerization temperature in the reaction for forming the trifluoropropylene oxide block unit is preferably -20 to 100 ° C, particularly preferably 0 to 50 ° C.

The polymerization reaction is an acid or an alkyl halide,
It is stopped by adding an aryl halide, an alkenyl halide or the like. The structure of the terminal group of the resulting fluorinated polyether can be adjusted depending on the type of the reaction terminator used. That is, when an acid is used as the reaction terminator, the reaction terminator becomes a hydroxyl group, and when an alkyl halide or alkenyl halide is used, the terminal has a structure such as an alkyl ether or an alkenyl ether. When an acrylic acid halide or a methacrylic acid halide is used as the terminating agent, an acryloyl group or a methacryloyl group is introduced at each end. By thus selecting the type of the polymerization terminator, a fluorine-containing polyether having a hydroxyl group or an alkyl ether, an alkenyl ether, acryloyl or methacryloyl at the terminal can be selectively obtained, which is also a major feature of the present invention. Is.

Acids used to stop the reaction include hydrochloric acid, sulfuric acid,
Examples thereof include acetic acid. Further, as the alkyl halide or alkenyl halide used for stopping the reaction,
Methyl iodide, ethyl iodide, propyl iodide, n-butyl iodide, tert-butyl iodide, methyl bromide, ethyl bromide, propyl bromide, n-butyl bromide, ter bromide
Examples thereof include t-butyl, allyl iodide, crotyl bromide, and the like, and acrylic acid halides such as acrylic acid chloride and methacrylic acid chloride, and methacrylic acid halides.

After the reaction is completed, the reaction is stopped with an acid, an alkyl halide, an alkenyl halide, a (meth) acrylic acid halide or the like, washed with water, the solvent is distilled off and, if necessary, dried under reduced pressure. A fluorinated polyether can be obtained.

When the star block polymer of the present invention thus obtained has an acryloyl group or a methacryloyl group at the terminal, the reactivity of the carbon-carbon double bond is utilized to further crosslink and cure. can do.
This curing reaction can be performed under heating and / or irradiation with light. In the case of curing by heating, the reaction can be promoted by performing it in the presence of a radical generator.

Examples of such radical generators include azobis compounds, peroxides, hydroperoxides and redox compounds. For example, azobisisobutyronitrile, 2,2'-azobis (2-
Amidinopropane) hydrochloride, ammonium persulfate, potassium persulfate, benzoyl peroxide, isopropyl percarbonate, methyl ethyl ketone peroxide, cumene hydroperoxide, dicumyl peroxide and the like can be mentioned.

The actinic ray used for curing by irradiation with light may be an energy ray that excites the curing reaction, but in general, ultraviolet rays or visible rays are preferable. Further, it is preferable to use a photopolymerization initiator during irradiation. Examples of the photopolymerization initiator include benzoin, 2-methylbenzoin, trimethylsilylbenzophenone, 4-methoxybenzophenone, benzoin methyl ether, acetophenone, anthraquinone, and 2,2.
-Dimethoxy-2-phenyl acetophenone, methyl benzoyl formate, etc. can be mentioned.

The star block polymer of the present invention obtained as described above is useful as a surface active agent or a material for electronic devices such as batteries, electrolytic capacitors, sensors and electrochromic elements, especially as an ion conductor.

The ionic conductor of the present invention may be composed of the star block polymer of the present invention and an alkali metal salt, and may further contain an organic solvent if necessary. When used as an ionic conductor, the mole fraction of trifluoropropylene oxide block units in the block polymer chain is preferably 0.4 to 0.9. If the mole fraction is less than 0.4, the mechanical strength will be weak and it will be difficult to form a film, and if it exceeds 0.9, it will be difficult to mix with the organic solvent.

Further, in the present invention, when a star block polymer having an acryloyl group or a methacryloyl group at the terminal is used as an ionic conductor, the molar amount of the trifluoropropylene oxide block unit in the block polymer chain is The rate is preferably 0.1 to 0.9. When the mole fraction is less than 0.1, the mechanical strength of the cured film is weak, and when it exceeds 0.9, it becomes difficult to retain the electrolytic solution. Then, the star-shaped block polymer before the curing reaction is made to contain an alkali metal salt, an organic solvent if necessary, and a polyether of the following formula (3) if necessary, and after adding a curing reaction additive, heating is performed. And / or it is preferably formed by irradiation with light. At this time, the ionic conductor can be formed as a thin film by casting or coating the above-mentioned curing composition on a substrate such as a metal such as aluminum, stainless steel or lithium foil, or glass and curing the composition. However, the ionic conductor of the present invention can be obtained by immersing the polymer in an electrolytic solution containing an alkali metal salt and optionally an organic solvent after curing the polymer.

[0033]

[Chemical 9]

(Wherein R ³ is an optionally substituted aliphatic hydrocarbon residue having 1 to 16 carbon atoms, OEt is an ethylene oxide unit, OPr is a propylene oxide unit, Ac is an acryloyl group or methacryloyl group, p is ≧ 1, q ≧
0 and r each represent an integer of 3 to 8) Each block of the polyether represented by the above formula (3) may be composed of ethylene oxide units and / or propylene oxide units, and both units may be random. Note that p and q are 1 ≦ p ≦ 200 and 0 ≦, respectively.
q ≦ 100 is preferable. When p and q exceed this value, the amount of terminal functional groups decreases and the crosslink density decreases, so the mechanical strength of the film becomes weak. In some cases, a polyether containing no acryloyl group or methacryloyl group may be mixed and used. When such a polyether is used in combination, it is advantageous in that the content of the organic solvent is improved.

In this case, it is 0 based on the entire polyether containing the star block polymer represented by the formula (1) having an acryloyl group or a methacryloyl group at the end of the present invention.
It can be used up to 90% by weight.

The organic solvent for the ionic conductor is a solvent that dissociates and solvates an alkali metal salt, and may be an organic solvent which is inert to the alkali metal salt. For example, ethylene carbonate, propylene carbonate, γ-butyrolactone,
An aprotic high dielectric constant solvent such as dimethyl sulfoxide or methylpyrrolidone is preferable. Further, in order to improve the electric conductivity, an aprotic low-viscosity solvent may be mixed and used with these solvents. Examples of such a low-viscosity solvent include diethyl carbonate, dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran and the like. In the present invention, a particularly preferable solvent is a mixed solvent of propylene carbonate and an aprotic low viscosity solvent.

The alkali metal salt for the ionic conductor is preferably Li salt or Na salt. Particularly preferred are Li salts, such as LiClO ₄ , LiCF ₃ SO
₃ , LiPF ₆ , LiBF ₄ , LiAsF ₆ , LiI and the like can be mentioned.

In the ionic conductor using the star block polymer of the present invention, the star block polymer is 20
˜90 wt%, 1 to 20 wt% alkali metal salt, and 0 to 70 wt% organic solvent are preferable. If the composition of the star block polymer is less than 20% by weight, it becomes impossible to form a film, and if it exceeds 90% by weight, the electrical conductivity is lowered, which is not preferable. The composition of the alkali metal salt is 1
If it is less than 20% by weight, the electric conductivity will decrease, and if it exceeds 20% by weight, an alkali metal salt will precipitate, which is not preferable. On the other hand, if the composition of the organic solvent exceeds 70% by weight, film formation becomes impossible. When the polymer terminal is an acryloyl group or a methacryloyl group, the star block polymer is 5 to 90% by weight, and the alkali metal salt is 1 to 20% by weight.
It is preferably composed by weight% and an organic solvent of 0 to 90 weight%. If the composition of the star block polymer is less than 5% by weight or more than 90% by weight and if the alkali metal salt is less than 1% by weight or more than 20% by weight, it is not preferable for the same reason as above. Also, if the composition of the organic solvent exceeds 90% by weight, the mechanical strength of the film after curing is lowered, which is not preferable.

The ionic conductor of the present invention can be formed into a film which is rich in flexibility and is not easily torn, and has a high electric conductivity, as described in the following examples.
In addition to lithium batteries, it is also useful as an ion conductor for electronic devices such as electrolytic capacitors, sensors and electrochromic devices.

[0040]

BEST MODE FOR CARRYING OUT THE INVENTION

Example 1 52.5 mg (0.936) of powdered potassium hydroxide
mmol) and pentaerythritol 398.2 mg
(2.925 mmol) was placed in a pressure-resistant airtight container under a nitrogen stream, and 10 ml (8.7 mmol) of dimethoxyethane was added. Then, 5.8 ml of ethylene oxide (117
mmol) and heated at 120 ° C. for 4 hours until the reaction was completed. The product was extracted with 100 ml of chloroform, dehydrated and desalted, and the solvent was distilled off under reduced pressure to obtain 5.59 g of star-shaped polyethylene oxide represented by the following formula (4).

[0041]

[Chemical 10]

Next, 1.85 g (0.975 mmol) of the above star-shaped polyethylene oxide was mixed with 218.8 mg (3.9 mmol) of powdered potassium hydroxide and 10 ml (8.7 mmol) of dimethoxyethane under a nitrogen stream. It was put in and stirred for 30 minutes. Next, 6.6 ml (78 mmol) of trifluoropropylene oxide was added, and the mixture was stirred for 60 hours while maintaining the liquid temperature at 20 to 40 ° C,
The reaction was terminated by adding 0.78 ml (3.9 mmol) of 5N hydrochloric acid. The product was extracted with 100 ml of chloroform, dehydrated and desalted, and the solvent was distilled off under reduced pressure to obtain a yellow paste product as a star block polymer of the following formula (5).
06 g (yield 67%) was obtained. The physical properties of the obtained block polymer are as follows.

[0043]

[Chemical 11]

The characteristics of the above block polymer are shown below.

(1) GPC peak molecular weight Shimadzu LC-9A was used for GPC column shode × K.
Two F806M (THF solvent) were used. The polystyrene conversion value was 3.1 × 10 ³ .

(2) ¹³ C-NMR (FIG. 1) It was measured in deuterated acetone using a GSX-270 type NMR measuring apparatus manufactured by JEOL Ltd. As a result, the following signals were observed.

47 ppm (quaternary carbon), 67 to 82 pp
m (--CH ₂ CH ₂ O-- which is the main chain and

[0048]

[Chemical 12]

(Structural carbon) 118 to 134 ppm (carbon of -CF ₃ group) (3) DSC TA Measured at a heating rate of 10 ° C./min using a DSC910 thermal analyzer manufactured by Instruments. The glass transition temperature was -26.34 ° C. Melting point is -20.76
C. (ethylene oxide block) and 69.52 ° C. (trifluoropropylene oxide block).

Example 2 Pentaerythritol 47.8 in the same manner as in Example 1.
15.8 mg (0.351 mmol) of potassium hydroxide
In the presence of mg (0.28 mmol), 7.0 ml (140 mmol) of ethylene oxide was polymerized in a solventless system to obtain 1.62 g (0.1%) of star-shaped polyethylene glycol.
17 mmol) powdered potassium hydroxide 26.3 mg
(0.468 mmol) and dimethoxyethane 10 ml
In the presence of (8.7 mmol), 4.0 ml (46.8 mmol) of trifluoropropylene oxide was reacted for 140 hours to obtain 5.15 g (yield 75%) of a white solid block polymer of the following formula (6). . The physical properties of the obtained block polymer are as follows.

(1) GPC peak molecular weight The polystyrene-converted mass was 2.2 × 10 ⁴ .

(2) ¹³ C-NMR (FIG. 2) 67-82 ppm (--CH ₂ CH ₂ O-- which is the main chain and

[0053]

[Chemical 13]

[0054] Carbon) 118~134ppm (-CF ₃ group carbons) (3) DSC glass transition temperature of the structure was -22.09 ℃.

The melting points were 42.94 ° C. (ethylene oxide block) and 68.86 ° C. (trifluoropropylene oxide block).

[0056]

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Example 3 1 g of a star block polymer (m = 10, n = 10 in the formula (5)) synthesized in the same manner as in Example 1 and LiC
The lO ₄ 0.068 g was dissolved in acetone 0.5 g. The entire solution was transferred to a glass petri dish (φ1 cm) and kept under vacuum at 100 ° C. for 15 hours to remove acetone. Semi-solid star block polymer and LiCl in the glass dish.
A mixture of O ₄ had precipitated. A half battery was prepared by sandwiching the mixture with metallic lithium (φ7.5 mm, t1.0 mm). AC impedance measurement of half battery (1 to 10 ⁵
Hz 26 ° C.) and the conductivity was calculated. Conductivity is 1 ×
It was 10 to ³ [S / cm].

Example 4 1 g of a star-shaped block polymer (m = 50, n = 100 in formula (5)) synthesized by the same method as in Example 1 and an electrolytic solution A (ethylene carbonate 46 wt%, propylene carbonate 46 w).
t%, LiClO ₄ 8 wt%) 1 g was dissolved in THF 98 g. 4.2 g of the solution was placed in a glass petri dish (φ3 cm) and kept under vacuum at room temperature for 2 hours. A thin film having a thickness of about 150 μm was formed in the glass petri dish. A half battery was prepared by sandwiching the thin film with metallic lithium (φ7.5 mm, t1.0 mm). AC impedance measurement of half battery (1
-10 ⁵ Hz 26 ° C.) and the conductivity was calculated. The conductivity was 6 × 10 ⁴ [S / cm].

Example 5 1 g of a star block polymer (m = 100, n = 100 in the formula (5)) synthesized by the same method as in Example 1 and a homopolymer of trifluoropropylene oxide (TFPO) (Mw = 1 × 10 ⁶ ) 1 g was dissolved in 98 g of THF. 8.9 g of the solution was put into a Teflon dish (φ5 cm) and kept at room temperature under vacuum for 1 hour and at 80 ° C. under vacuum for 1 hour.
A thin film having a thickness of about 20 μm was formed in the Teflon dish. The thin film was immersed in the electrolytic solution A at 80 ° C. for 7 hours.
The thin film after immersion contained about 40 wt% of the electrolytic solution A. This thin film was molded into a circular shape of φ7.5 mm, and a half battery was prepared by sandwiching it with metallic lithium (φ7.5 mm, t1.0 mm). AC impedance measurement of half battery (1-10
⁵ Hz 26 ° C.) was performed to calculate the conductivity. Conductivity is 2
It was × 10 to ⁴ [S / cm]. On the other hand, the length of this thin film is 1
It was molded into 0 mm and a width of 5 mm, and the dynamic viscoelasticity was measured.
The dynamic elastic modulus was 6 × 10 ⁷ [dyne / cm ² ].

Example 6 31.5 g (19.5 g) of polyethylene glycol obtained by polymerizing 30 molecules of ethylene oxide on trimethylolpropane.
powdery potassium hydroxide 3.8 g (58.5 mmol)
mmol) and 60 ml of dimethoxyethane in the presence of 10 ml of trifluoropropylene oxide (117 mmo
l) was reacted at a temperature of 20 to 40 ° C. for 69 hours, and then 4.7 ml (58.5 mmol) of acrylic acid chloride was added to complete the reaction. 32.4 g (yield 73%) of a block polymer of a pale yellow transparent liquid of the following formula (7) was obtained.

[0061]

[Chemical 15]

The physical properties of the obtained block polymer are as follows.

(1) GPC peak molecular weight The polystyrene reduced mass was 3.3 × 10 ³ .

(2) ¹³ C-NMR 9 to 24 ppm (carbon of --CH ₂ CH ₃ group) 45 ppm

[0065]

Embedded image

65-80 ppm (--CH ₂ C which is the main chain)
H ₂ O-and

[0067]

[Chemical 17]

Structure carbon) 120 to 132 ppm (carbon of --CF ₃ group and --CH =
CH ₂ group carbon) 167ppm

[0069]

Embedded image

168, 166 ppm (carbon as unreacted raw material) (3) DSC Melting point was -2.5 ° C.

Example 7 The acrylated polyethylene oxide-polytrifluoropropylene oxide block polymer (EO-TFPO block polymer) synthesized in Example 6.
1 g of (formula (7)), 4 g of electrolytic solution B (trifluoropropylene carbonate (TFPC) solution containing 1 M / l LiPF ₆ ) and 0.03 g of methylbenzoyl formate were mixed well. The solution was sandwiched between fluorescent glass (made by Matsunami Glass) and the film thickness was adjusted with a Teflon sheet having a thickness of 0.2 mm. The solution was exposed with a high pressure mercury lamp. Exposure amount is about 20 J /
cm ² . The solution formed a film. The conductivity of the film is 5 × 10 to ⁴ S / cm, and the dynamic elastic modulus is 9 ×.
It was 10 ⁵ [dyne / cm ² ].

Example 8 Instead of the electrolytic solution B, electrolytic solution C (TFPC / propylene carbonate (PC) containing 1 M / l LiPF ₆ (weight ratio 1:
Evaluation was made in the same manner as in Example 7 except that 1) the solution) was used. The conductivity of the film was 9 × 10 ⁴ S / cm, and the dynamic elastic modulus was 1 × 10 ⁶ [dyne / cm ² ].

Example 9 Instead of the electrolytic solution B, an electrolytic solution D (ethylene carbonate (EC) containing 1 M / l LiPF ₆ / propylene carbonate (PC)) was used.
Evaluation was made in the same manner as in Example 7 except that the (weight ratio 1: 1) solution was used. The conductivity of the film is 3 × 10 ~ ³ S / c
m, the dynamic elastic modulus was 3 × 10 ⁵ [dyne / cm ² ].

Example 10 Acrylated EO synthesized in the same manner as in Example 6
-TFPO block polymer (m = 10, n = 4) 0.
7 g, 0.3 g of trifunctional polyethylene oxide (PEO) acrylate represented by the following formula (8), 4 g of electrolytic solution D, and 0.03 g of methylbenzoyl formate were mixed well. A film was formed from the solution in the same manner as in Example 7. The conductivity of the film is 2 × 10 ³ S / cm, and the dynamic elastic modulus is 3 × 1.
It was 0 ⁵ [dyne / cm ² ].

[0075]

[Chemical 19]

Example 11 (1) 2.25 g of LiCoO ₂ , acetylene black
25 g, PEO (average molecular weight 4,000,000) 0.
10 g, electrolytic solution D 0.40 g, acetonitrile 10 ml
The suspension mixed with was printed on a SUS plate and dried at room temperature for 3 hours, and then the pre-curing stock solution of Example 10 was applied on the surface and exposed under a nitrogen gas atmosphere with a high pressure mercury lamp to obtain 1.8 cm × 2.8 c.
m positive electrode was produced. The exposure amount was about 20 J / cm ² .

(2) A Li foil was used and pressure bonded to a copper plate to prepare a negative electrode.

(3) The film obtained in Example 10 (film thickness 10
0 μm) and the positive and negative electrodes prepared in (1) and (2) were combined to prepare a flat plate battery. Using the produced battery, a constant current (0.5 mA / cm ² ) charge / discharge cycle test was performed at 25 ° C. The charging / discharging conditions were such that the final charge voltage was 4.2V and the final discharge voltage was 3.0V. The battery capacity in the 5th cycle is
The charge was 2.29 mAh and the discharge was 2.27 mAh.

Example 12 The temperature dependence of the conductivity of the film used in Example 9 was measured. For comparison, the temperature dependence of the electrical conductivity of a film prepared from the trifunctional polyethylene oxide (PEO) acrylate represented by the following formula (8) in the same manner as in Example 7 was also measured.

[0080]

[Table 1]

As can be seen from the above, when the product of the present invention is used, a film having high conductivity can be obtained even at a low temperature.

[0082]

Embedded image

[0083]

Industrial Applicability As described above, the star block polymer of the present invention contains an ethylene oxide block unit and a trifluoropropylene oxide block unit, which has a high conductivity ion conductivity for lithium batteries and the like. It is useful as a body.

[Brief description of drawings]

FIG. 1 ¹³ C-NMR spectrum of the star block polymer of the present invention obtained in Example 1,

FIG. 2 ¹³ C-NMR spectrum of the star block polymer of the present invention obtained in Example 2,

FIG. 3 ¹³ C-NMR spectrum of the star block polymer of the present invention obtained in Example 6,

FIG. 4 is a graph showing charge / discharge characteristics at the 5th cycle of the battery subjected to the charge / discharge test in Example 11.

Claims (10)

[Claims] 1. A star block polymer represented by the following formula (1). Embedded image (In the formula, R ¹ represents an optionally substituted aliphatic hydrocarbon residue having 1 to 16 carbon atoms, R ² represents hydrogen, an optionally substituted alkyl group having 1 to 16 carbon atoms, an alkenyl group, or fluorine. A substituted alkyl group, a fluorine-substituted alkenyl group, a phenyl group, an alkyl-substituted phenyl group, an acryloyl group, and a methacryloyl group are shown, and m ≧ 1, n ≧ 1, and L = an integer of 3 to 8) 2. The star block polymer according to claim 1, wherein R ² in the formula (1) is an acryloyl group or a methacryloyl group. 3. An adduct having an ethylene oxide block unit obtained by adding ethylene oxide to a polyhydric alcohol having 3 to 8 hydroxyl groups, which is represented by the following formula (2) in the presence of an alkali metal hydroxide. The method for producing a star block polymer according to claim 1, wherein trifluoropropylene oxide is added and reacted to form a trifluoropropylene oxide block unit, and then the reaction is stopped. Embedded image 4. An ionic conductor, characterized in that the star block polymer of the formula (1) according to claim 1 contains an alkali metal salt. 5. An ionic conductor, wherein the star block polymer of the formula (1) according to claim 1 contains an alkali metal salt and an organic solvent. 6. An ion conductor comprising the crosslinked polymer of the star block polymer according to claim 2 and an alkali metal salt. 7. An ionic conductor comprising the cross-linked polymer of the star block polymer according to claim 2, an alkali metal salt and an organic solvent. 8. An ionic conductor comprising a crosslinked star-shaped block polymer according to claim 2, which is mixed with a star-shaped polyether represented by the following formula (3), and an alkali metal salt. Embedded image (In the formula, R ³ is an optionally substituted aliphatic hydrocarbon residue having 1 to 16 carbon atoms, OEt is an ethylene oxide unit,
OPr is a propylene oxide unit, Ac is an acryloyl group or methacryloyl group, p ≧ 1, q ≧ 0, and r is 3
~ Indicates an integer of 8) 9. An ion conductor comprising a star-shaped block polymer cross-linked polymer according to claim 2, which is mixed with a star-shaped polyether represented by the following formula (3), an alkali metal salt and an organic solvent. . [Chemical 4] (In the formula, R ³ is an optionally substituted aliphatic hydrocarbon residue having 1 to 16 carbon atoms, OEt is an ethylene oxide unit,
OPr is a propylene oxide unit, Ac is an acryloyl group or methacryloyl group, p ≧ 1, q ≧ 0, and r is 3
~ Indicates an integer of 8) 10. A lithium battery containing at least one kind of the ionic conductor according to claim 4.