JP6273749B2 - Network polymers and polymer gel electrolytes - Google Patents

Description

  The present invention relates to a novel network polymer having a crown ether, a polymer gel electrolyte containing a network polymer, and a secondary battery containing the polymer gel electrolyte.

  Conventionally, gel materials have been widely used in foods, medical products, daily necessities, industrial products, etc., and the types of polymer compounds used in these materials are also diverse. There are only two types: gels and chemical gels.

A physical gel is a gel that is often found in nature, such as gelatin and agar, and a large variety of physical gels occupy most of the living tissue.
Since such a physical gel forms a network by physical attractive interaction acting between polymers, the stability to temperature and solvent is low.

On the other hand, a chemical gel is a huge single molecule in which the entire network is directly connected by a covalent bond. Therefore, the chemical gel is excellent in temperature and solvent stability, and is widely used in industrial applications.
However, the chemical gel has a drawback that since the cross-linking points are fixed, the non-uniform structure formed in the cross-linking reaction is permanently retained, and the mechanical strength is extremely low.

On the other hand, in recent years, a new type of gel that is not classified as either a physical gel or a chemical gel using a novel method, that is, a “ringing gel” or a “topological gel” has been proposed. Polyrotaxane is used for the moving gel.
This polyrotaxane penetrates through an opening of a cyclic compound (rotor) in a straight line with a linear molecule (axis: axis) so that the cyclic compound includes the linear molecule and the cyclic compound is not detached. As described above, there are disclosed cross-linked polyrotaxanes in which blocking groups are arranged at both ends of a linear molecule, which are formed by crosslinking a plurality of such polyrotaxanes and applicable to a tumbling gel (see Patent Documents 1 to 9). ).

  This crosslinked polyrotaxane has viscoelasticity because a cyclic compound penetrating through a linear molecule can move along the linear molecule (pulley effect), and even if tension is applied, Since the tension can be uniformly dispersed by the pulley effect, unlike the conventional crosslinked polymer, it has an excellent property that cracks and scratches are hardly generated.

However, these cross-linked polyrotaxanes have problems such as low stimulus responsiveness and requiring multiple steps for production.
For these crosslinked polyrotaxanes, the present inventors have reported a gel composed of a polymer compound obtained by polymerizing pseudorotaxane (Non-patent Document 1). Since the polymer compound is easy to produce, further application is expected.

  On the other hand, as an application field of the gel material, development of a gel electrolyte obtained by gelling an electrolyte solution used for a lithium ion secondary battery or the like has been studied. For example, in Patent Documents 10 and 11, an electrolyte is mixed with a polymer such as polyvinylidene fluoride (PVDF) or polyacrylonitrile (PAN), heated to dissolve the polymer in the electrolyte, and then cooled to gel. Is disclosed.

  Batteries using these gel electrolytes have the advantage that liquid leakage is unlikely to occur because the electrolyte is held by the gel. However, in the conventional gel electrolyte, since the amount of the electrolytic solution used is large and the thermal stability is insufficient, there is still a demand for improvement in terms of safety.

  In order to solve the above problems, the present inventors have succeeded in constructing a novel network polymer having a rotaxane structure using a crown ether for the purpose of obtaining a polymer gel electrolyte having both high safety and high ionic conductivity. In addition, it has been found that the polymer gel electrolyte obtained from the network polymer has both high safety and high ionic conductivity (Patent Document 12).

  One of the batteries that are currently expected as the next-generation secondary battery is a multivalent ion battery. For example, a magnesium ion secondary battery using divalent (polyvalent) magnesium as the negative electrode active material can be expected to improve energy density compared to a lithium ion secondary battery using monovalent lithium as the negative electrode active material. . In current electric vehicles, the travel distance by the lithium ion secondary battery is about 150 km, but the travel distance can be extended by increasing the energy density of the secondary battery.

On the other hand, magnesium metal has a problem that it forms a passive film at room temperature and does not lead to a reversible dissolution and precipitation reaction, and a magnesium ion secondary battery has not yet reached a practical stage. As one of the solutions, an electrolytic solution in which a Grignard reagent and an organic metal compound (for example, C ₆ H ₅ MgCl) or a salt other than magnesium (for example, (C ₂ H ₅ ) ₂ AlCl) are dissolved in tetrahydrofuran is used. (Patent Document 13).

  The inventors have so far used a non-aqueous ammonium ionic liquid solution of a Grignard reagent as an electrolyte solution, which is superior to the case of a Grignard reagent alone, has high ionic conductivity, and is excellent. Have found an electrolyte solution for magnesium ion secondary battery that exhibits reversibility of dissolution and precipitation of magnesium (Non-Patent Document 2).

  Furthermore, the inventors have also found an electrolytic solution for a magnesium ion secondary battery comprising an imidazolium ionic liquid or a pyrrolidinium ionic liquid and a Grignard reagent (Patent Document 14).

  However, the Grignard reagent has a problem of high reactivity and high possibility of causing a major accident due to liquid leakage. In order to prevent liquid leakage, it is effective to use a polymer gel electrolyte as in the case of the lithium ion secondary battery. However, a network polymer such as a normal acrylic resin has a low resistance to a Grignard reagent and decomposes.

Japanese Patent No. 3475252 JP 2005-068032 A WO 2006/115255 WO2009 / 136618 JP 2009-270120 A JP 2009-051994 JP 2010-155880 A JP 2010-159336 A JP 2010-159337 A JP 2002-334690 A JP 2003-317692 A WO2013 / 099224 JP 2007-188709 A JP 2012-48874 A

Polymer Journal, Vol.40, No.3, (2008), 205-211. J. Power Sources, 195, (2010), 2096-2098.

  The present invention has been made in view of such circumstances, and in order to obtain a polymer gel electrolyte having both higher safety and higher fastness and higher ionic conductivity, a plurality of cyclic compounds are linear. An object is to obtain a novel network polymer having a rotaxane structure penetrated in a skewered manner in a compound.

  As a result of intensive studies to solve the above-mentioned problems, the present inventor succeeded in the construction of a novel network polymer having a rotaxane structure in which a plurality of cyclic units are skewered into linear units, and the network polymer However, it has high safety and high fastness that can withstand the high reactivity of organomagnesium halides such as Grignard reagents, and a solution of organomagnesium halides obtained from the network polymer of the present invention is used as an electrolyte. As a result, the present inventors have found that the polymer gel electrolyte has high ionic conductivity, and has completed the present invention.

That is, the present invention provides (1) the following formula (I)
(Wherein R ¹ , R ² and R ³ are the same or different and each represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 15 carbon atoms which may have —O—, m Represents an integer of 1 to 10, and when m is 2 or more, each R ² may be the same or different, Z ⁻ represents a counter anion, and a plurality of Z ⁻ are the same or different. Or the following formula (I ′)
(In the formula, R ¹ , R ² , R ³ , and m are the same as defined in formula (I), and R ⁴ and R ⁵ are the same or different and represent a residue derived from an electrophile. Per unit of linear unit represented by the following formula (II)
(In the formula, R ⁶ and R ⁷ are the same or different and each represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 15 carbon atoms which may have -O-; Or 1 to (m + 1) units (where m is the same as m in formula (I)) of the cyclic unit represented by Network polymer,
(2) The network polymer according to (1), which has 2 to 1000 units (A),
(3) The cyclic unit represented by the formula (II) is represented by the following formula (III)
(In the formula, R ⁶ and R ⁷ are the same or different and each represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 15 carbon atoms which may have -O-; A network polymer according to (1) or (2), characterized in that it is a unit represented by the following formula:
(4) The unit represented by the formula (III) is represented by the following formula (IV)
(In the formula, n3 and n4 are the same or different and each represents an integer of 1 to 14, and the dotted line portion indicates that it is bonded to either the 3-position or 4-position of the benzene ring). The network polymer according to (3), which is a unit represented by:
(5) The linear unit represented by the formula (I) is represented by the following formula (V)
(Wherein R ¹ , R ² , R ³ , and Z ⁻ are the same as defined in formula (I)), and any one of (1) to (4) It relates to the network polymer as described above.

The present invention also provides:
(6) Step (1): Formula (VI)
(Wherein R ¹ , R ² and R ³ are the same or different and each represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 15 carbon atoms which may have —O—, m Represents an integer of 1 to 10, and when m is 2 or more, each R ² may be the same or different, Z ⁻ represents a counter anion, and a plurality of Z ⁻ are the same or different. A linear compound represented by:
Formula (VII) below
(In the formula, R ⁶ and R ⁷ are the same or different and each represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 15 carbon atoms which may have -O-; Or represents an integer of 4.) and a cyclic compound represented by
For one molecule of the linear compound represented by the formula (VI), 1 to (m + 1) molecules of the cyclic compound represented by the formula (VII) (where m is the same as m in the formula (VI)). A compound (A ′) having a structure formed by inclusion in a skewered manner, and
Step (2): The method for producing a network polymer according to any one of (1) to (5), which comprises a step of subjecting the compound (A ′) to olefin metathesis polymerization,
(7) After step (1) or step (2),
Step 3: The product is reacted with an electrophile,
Formula (I)
Wherein R ¹ , R ² and R ³ are the same or different and each represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 15 carbon atoms which may have —O—, m represents an integer of 1 to 10, and when m is 2 or more, each R ² may be the same or different, Z ⁻ represents a counter anion, and a plurality of Z ⁻ may be the same or different. A unit represented by the formula (I ′)
(In the formula, R ¹ , R ² , R ³ , and m are the same as defined in formula (I), and R ⁴ and R ⁵ are the same or different and represent a residue derived from an electrophile. It has the process of converting into the unit represented by this, It is related with the manufacturing method of the network polymer as described in (6) characterized by the above-mentioned.

Furthermore, the present invention provides
(8) A polymer gel electrolyte containing the network polymer according to any one of (1) to (5) in the electrolytic solution,
(9) The polymer gel electrolyte according to (8), wherein the electrolytic solution is a diethylmethylmethoxyethylammonium bis (trifluoromethane) sulfonimide salt solution of ethylmagnesium bromide,
(10) A secondary battery using the polymer gel electrolyte according to (8) or (9).

  The network polymer gel of the present invention contains a rotaxane structure composed of an inclusion structure formed from a specific linear unit having a crosslinking point and a cyclic unit, so that the temperature or High stability and mechanical strength against solvents. In addition, since multiple cyclic units are included in the linear unit of the rotaxane structure, even when using a highly reactive electrolytic solution, high safety and high robustness compared to conventional network polymer gels Have By using the network polymer gel of the present invention as a polymer gel electrolyte, it is possible to obtain a higher ion transport efficiency than a normal network polymer and to minimize the amount of electrolyte used.

1 is a ¹ H-NMR spectrum of 1,2-bis (N- (10-undecen-1-yl) aminoethoxy) ethane dihexafluorophosphoric acid. FIG. 1 is an IR spectrum of 1,2-bis (N- (10-undecen-1-yl) aminoethoxy) ethane dihexafluorophosphoric acid. FIG. It is a figure which shows the < ¹ > H-NMR spectrum of bis (10-undecenyloxymethylbenzo) -24-crown-8-ether. 1 is a diagram showing an IR spectrum of a network polymer of Example 1. FIG. It is a figure which shows the result of the stability test with respect to the Grignard reagent of the network polymer (ether type) of this invention, and the network polymer (ester type) of a prior art.

1 Network Polymer The network polymer of the present invention comprises a linear unit represented by the above formula (I) or formula (I ′) and a cyclic unit represented by the above formula (II) clasped in a skewered manner. Unit (A).
Moreover, the network polymer of this invention may contain the linear compound represented by following formula (I) and formula (I ') simultaneously in the same polymer.

(Linear unit represented by Formula (I) or Formula (I ′))
In the linear unit represented by the formula (I) or the formula (I ′), R ¹ , R ² and R ³ may have a substituted or unsubstituted carbon atom having 1 to 15 carbon atoms. In the “divalent hydrocarbon group”, the “divalent hydrocarbon group having 1 to 15 carbon atoms” includes methylene group, dimethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene. Group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, tridecamethylene group, tetradecamethylene group, pentadecamethylene group, and other alkylene groups.

  In addition, when the “hydrocarbon group having 1 to 15 carbon atoms” has “—O—”, the following formula having one or more “—O—” at the terminal and / or inside of the hydrocarbon group: The group represented by (VIII) may be sufficient.

In the formula, s1 to sn are natural numbers, s1 + s2 +... + Sn is an integer of 1 to 15, t to t (sn + 1) is 0 or 1, provided that at least one of t to t (sn + 1) is 1. Yes, each hydrogen atom in (CH ₂ ) may be substituted with an alkyl group having 1 to 10 carbon atoms.

  Specific examples of the “C1-C15 hydrocarbon group” having one “—O—” represented by the formula (VIII) include a methyleneoxy group, a dimethyleneoxy group, a trimethyleneoxy group, tetra Methyleneoxy group, pentamethyleneoxy group, hexamethyleneoxy group, heptamethyleneoxy group, octamethyleneoxy group, nonamethyleneoxy group, decamethyleneoxy group, undecamethyleneoxy group, dodecamethyleneoxy group, tridecamethyleneoxy group , Tetradecamethyleneoxy group, pentadecamethyleneoxy group, methyleneoxymethylene group, dimethyleneoxymethylene group, trimethyleneoxymethylene group, tetramethyleneoxymethylene group, pentamethyleneoxymethylene group, hexamethyleneoxymethylene group, heptamethylene Oxymethylene group, octame Tyleneoxymethylene group, nonamethyleneoxymethylene group, decamethyleneoxymethylene group, undecamethyleneoxymethylene group, dodecamethyleneoxymethylene group, tridecamethyleneoxymethylene group, tetradecamethyleneoxymethylene group, methyleneoxydimethylene group, Dimethyleneoxydimethylene group, trimethyleneoxydimethylene group, tetramethyleneoxydimethylene group, pentamethyleneoxydimethylene group, hexamethyleneoxydimethylene group, heptamethyleneoxydimethylene group, octamethyleneoxydimethylene group, nona Examples include a methyleneoxydimethylene group, a decamethyleneoxydimethylene group, an undecamethyleneoxydimethylene group, a dodecamethyleneoxydimethylene group, and a tridecamethyleneoxydimethylene group.

  In addition, the “hydrocarbon group having 1 to 15 carbon atoms” having two “—O—” represented by the formula (VIII) is specifically a methyleneoxydimethyleneoxy group, dimethyleneoxydimethyleneoxy. Group, trimethyleneoxydimethyleneoxy group, tetramethyleneoxydimethyleneoxy group, pentamethyleneoxydimethyleneoxy group, hexamethyleneoxydimethyleneoxy group, heptamethyleneoxydimethyleneoxy group, octamethyleneoxydimethyleneoxy group, Nonamethyleneoxydimethyleneoxy group, decamethyleneoxydimethyleneoxy group, undecamethyleneoxydimethyleneoxy group, dodecamethyleneoxydimethyleneoxy group, tridecamethyleneoxydimethyleneoxy group, dimethyleneoxydimethyleneoxy group, Dimethyleneoxytrimethyle Oxymethylene group, dimethyleneoxytetramethyleneoxy group, dimethyleneoxypentamethyleneoxy group, dimethyleneoxyhexamethyleneoxy group, dimethyleneoxyheptamethyleneoxy group, dimethyleneoxyoctamethyleneoxy group, dimethyleneoxynonamethyleneoxy group , Dimethyleneoxydecamethyleneoxy group, dimethyleneoxyundecamethyleneoxy group, dimethyleneoxide decamethyleneoxy group, dimethyleneoxytridecamethyleneoxy group, methyleneoxydimethyleneoxymethylene group, dimethyleneoxydimethyleneoxymethylene Group, trimethyleneoxydimethyleneoxymethylene group, tetramethyleneoxydimethyleneoxydimethyleneoxymethylene group, pentamethyleneoxydimethyleneoxymethylene group, hexamethyl Noxydimethyleneoxymethylene group, heptamethyleneoxydimethyleneoxymethylene group, octamethyleneoxydimethyleneoxymethylene group, nonamethyleneoxydimethyleneoxymethylene group, decamethyleneoxydimethyleneoxymethylene group, undecamethyleneoxydimethylene Oxymethylene group, dodecamethyleneoxydimethyleneoxymethylene group, dimethyleneoxydimethyleneoxydimethylene group, dimethyleneoxytrimethyleneoxydimethylene group, dimethyleneoxytetramethyleneoxydimethylene group, dimethyleneoxypentamethyleneoxydi Methylene group, dimethyleneoxyhexamethyleneoxydimethylene group, dimethyleneoxyheptamethyleneoxydimethylene group, dimethyleneoxyoctamethyleneoxydimethylene group Dimethylene oxy nonamethylene oxy dimethylene group, dimethylene oxy decamethylene oxy dimethylene group, there may be mentioned a dimethylene oxy undecamethylene oxy dimethylene group such as but not limited to.

Further, the hydrocarbon group having 1 to 15 carbon atoms of the R ^1, R ² and R ³ may be a straight chain, may have a branched chain. As the hydrocarbon group of the branched chain portion, a rotaxane structure composed of a linear unit represented by the formula (I) or the formula (I ′) and a cyclic unit represented by the formula (II), Any hydrocarbon group may be used as long as the cyclic unit represented by formula (I) can move freely on the linear unit represented by formula (I) or formula (I ′). Group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, i-butyl group, tert-butyl group, pentyl group, neopentyl group, amyl group, hexyl group, cyclohexyl group, C1-C10 alkyl groups, such as a heptyl group, an octyl group, a nonyl group, a decanyl group, are mentioned, From the point of a steric hindrance etc., a methyl group, an ethyl group, n-propyl group, n-butyl group is preferable, A methyl group is most preferred.

The group represented by R ¹ and R ³ is preferably an octamethylene group, nonamethylene group, decamethylene group, octamethyleneoxymethylene group, nonamethyleneoxymethylene group, decamethyleneoxymethylene group, more preferably octamethylene. An oxymethylene group, a nonamethyleneoxymethylene group and a decamethyleneoxymethylene group are preferred, and a nonamethyleneoxymethylene group is most preferred.

In addition, the group represented by R ² is preferably a hexamethylene group, a heptamethylene group, an octamethylene group, a dimethyleneoxydimethyleneoxydimethylene group, a dimethyleneoxytrimethyleneoxydimethylene group, or trimethyleneoxydi. A methyleneoxytrimethylene group, more preferably a hexamethylene group, an octamethylene group, and a dimethyleneoxydimethyleneoxydimethylene group, and most preferably a dimethyleneoxydimethyleneoxydimethylene group.
Examples of the substituent in the “substituted or unsubstituted hydrocarbon group having 1 to 15 carbon atoms” include an alkoxy group. Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, and a sec-butoxy group.

In the linear unit represented by the formula (I), the counter ion represented by Z ⁻ is a linear unit represented by the formula (I) at the opening of the cyclic unit represented by the formula (II). A rotaxane structure or a pseudo-rotaxane structure in which units are included in a skewered manner can be constructed, and -N ⁺ H _2- in the unit represented by the formula (I) in the rotaxane structure or the pseudo-rotaxane structure The group is not limited as long as it is a monovalent anion capable of converting a group into a —NR ⁴ — and / or —NR ⁵ — group (R ⁴ and R ⁵ represent a residue derived from an electrophile). Specifically, BF ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , PCl ₆ ⁻ , BCl ₄ ⁻ , AsCl ₆ ⁻ , SbCl ₆ ⁻ , TaCl ₆ ⁻ , NbCl ₆ ⁻ , PBr ₆ ⁻ , BBr ₄ ⁻ , AsBr _{^{6 -, AlBr 4 -, TaBr}} 6 -, NbBr 6 -, SbF 6 -, AlF 4 -, ClO 4 -, AlCl 4 -, TaF 6 -, NbF 6 -, CN -, F (HF) m - ( the In the formula, m represents a numerical value of 1 or more and 4 or less.), N (RfSO ₃ ) ₂ ⁻ , C (RfSO ₃ ) ₃ ⁻ , RfSO ₃ ⁻ , RfCO ₂ ⁻ , N (SO ₂ F) ₂ ^{— and the} like. ^{_{mentioned, N (RfSO 3) 2 -}} , C (RfSO 3) 3 -, RfSO 3 - or RfCO ₂ ^- Rf contained in the anions represented by represents a fluoroalkyl group having 1 to 12 carbon atoms, Specific examples include fluorinated alkyl groups such as trifluoromethyl, pentafluoroethyl, heptafluoropropyl and nonafluorobutyl. Of the Z ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , PCl ₆ ⁻ , BCl ₄ ⁻ and AsCl ₆ ⁻ are preferable, BF ₄ ⁻ , PF ₆ ⁻ and PCl ₆ ⁻ are more preferable, and PF ₆ ⁻ Is most preferred.

In the linear unit represented by the formula (I ′), the “residue derived from electrophile” of R ⁴ and R ⁵ is the linear unit represented by the formula (I ′) and the formula (II In the rotaxane structure composed of the cyclic unit represented by formula (II), any group can be used as long as the cyclic unit represented by formula (II) can move freely on the linear unit represented by formula (I ′). Specifically, alkyl groups such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, i-butyl group, tert-butyl group, Vinyl group, 1-propenyl group, allyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1,3-butanedienyl group, 1-ethylvinyl group, 1-methyl-1-propenyl Group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, etc. Alkynyl groups such as alkenyl group, ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1,3-butanediynyl group, 1-methyl-2-propynyl group, etc. In view of steric hindrance and the like, a methyl group, an ethyl group, a vinyl group, an ethynyl group, an n-propyl group, and an n-butyl group are preferable, a methyl group and a vinyl group are more preferable, and a methyl group is most preferable.

  In the linear unit represented by the formula (I) and the formula (I ′), m may be any natural number as long as the cyclic unit represented by the formula (II) is included in a skewered manner. However, Preferably it is 1-10, More preferably, it is 1-3.

  The linear unit represented by the formula (I) is preferably the formula (V)

In which R ¹ , R ² , R ³ , and Z ⁻ are the same as defined in formula (I).

More preferably, the formula (Va)

Wherein Z ⁻ is the same as defined in formula (I).

Most preferably, the formula (Vb)

It is a compound represented by these.
The linear unit represented by the formula (I ′) is preferably the formula (V ′)

Wherein R ¹ , R ² , and R ³ are the same as defined in formula (I).

More preferably, the formula (Va ′)
It is a compound represented by these.

(Cyclic unit represented by formula (II))
The cyclic unit represented by the formula (II) represented by R ⁶ and R ⁷ is a linear or branched divalent hydrocarbon having 1 to 15 carbon atoms, which may have —O—. Examples of the “group” include the same groups as R ¹ , R ² and R ^{3 in the} formula (I) or (I ′).

  The cyclic unit represented by the formula (II) is preferably the formula (III)

In which R ⁶ and R ⁷ are the same or different and may be —O— substituted or unsubstituted divalent hydrocarbon group having 1 to 15 carbon atoms. The dotted line part indicates that it is bonded to either the 3-position or 4-position of the benzene ring.

  More preferably, the formula (IV)

In the formula, the dotted line part indicates that it is bonded to either the 3-position or the 4-position of the benzene ring, and n3 and n4 are 1 to 15 at the same time.

  More preferably, the formula (IVa)

In the formula, the dotted line part indicates that it is bonded to either the 3-position or the 4-position of the benzene ring, and n3 and n4 are 6 to 10 at the same time.

  Most preferably, the formula (IVb)

It is a unit represented by.

(Structure and physical properties of network polymer)
The “network polymer” of the present invention has a rotaxane structure. In rotaxane, the linear unit represented by the formula (I) penetrates the cyclic unit represented by the formula (II), and the bulky sites are bonded to both ends of the shaft composed of the linear unit. This means that the ring cannot be removed from the axis due to steric hindrance. The bulky part is called a stopper or cap, an end group. On the other hand, when there is no stopper or when there is a stopper, the bulkiness is insufficient, which is called pseudorotaxane.
The network polymer has no stopper component and is constructed from a ring component and a linear component, but another pseudo-rotaxane unit bonded to another pseudo-rotaxane unit by constituting a network plays the role of a stopper, The ring and shaft are not separated.

In the “network polymer” of the present invention, the ratio of the linear unit represented by the formula (I) or the formula (I ′) to the cyclic unit represented by the formula (II) is 1 linear unit. On the other hand, the cyclic unit is 1 to (m + 1) (where m + 1 corresponds to the number of N atoms in the linear unit), but preferably the cyclic unit is 1 unit of the linear unit. 2 to 10 units, more preferably 2 to 4.
Moreover, the number of cyclic units represented by the formula (II) may be different or the same for each linear unit represented by the formula (I) or the formula (I ′).

  The “network polymer” of the present invention includes hydrocarbons such as water and n-hexane; halogenated hydrocarbons such as chloroform and dichloromethane; aromatic hydrocarbons such as benzene and toluene; alcohols such as methanol and ethanol. Ketones such as acetone; ethers such as tetrahydrofuran and diethyl ether; insoluble in solvents such as acetonitrile, N, N-dimethylformamide and ethyl acetate.

The network polymer of the present invention has very low solubility in a solvent, and it is extremely difficult to measure the number average molecular weight, weight average molecular weight, viscosity average molecular weight, etc. of the synthesized polymer.
The degree of polymerization is about 2 to 1,000, preferably 300 to 800, and most preferably 500 to 600. The degree of polymerization of the polymer depends on the solubility of the synthesized polymer in the reaction solvent during the olefin metathesis polymerization, and the degree of polymerization of the polymer can be adjusted by the reaction solvent used.

  The glass transition point of the network polymer of the present invention is preferably 10 ° C to -40 ° C, more preferably 0 ° C to -30 ° C, and further preferably -10 ° C to -30 ° C. The glass transition point of the network polymer of the present invention can be measured by a well-known technique such as differential scanning calorimetry (DSC).

  Furthermore, in the network polymer of the present invention, the swelling degree of 1M lithium hexafluorophosphate with respect to a mixed solvent of ethylene carbonate (EC) -dimethyl carbonate (DMC) (EC: DMC-1: 1) at 25 ° C. is preferably 30%. ~ 100%, most preferably about 50% -60%.

The degree of swelling [%] was calculated by the following formula.

The network polymer of the present invention and the network polymer after neutralization described later have gelation ability with respect to various organic solvents. Examples of the organic solvent include protic organic solvents such as fatty acids, aliphatic alcohols, and phenol derivatives, non-lime such as glyme, alkene carbonate, alkyl carbonate, cyclic ether, amides, nitriles, ketones, and esters. Examples include protic organic solvents. Specifically, propylene carbonate, ethylene carbonate, diethyl carbonate, γ-butyrolactone, 1,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, dimethyl sulfoxide, 1,3-dioxolane, formamide, dimethylformamide, 1,4- Phosphoric triester derivatives such as dioxane, acetonitrile, nitromethane, ethyl monoglyme, trimethyl phosphate, trimethoxymethane, dioxolane derivatives, sulfolane, 3-methyl-2-oxazolidinone, propylene carbonate derivatives, tetrahydrofuran derivatives, diethyl ether, Examples include aprotic organic solvents such as 1,3-propane sultone. These can also be used in mixture of 2 or more types.
In addition, the network polymer of the present invention and the network polymer after neutralization have gelling ability with respect to various ionic liquids. The ionic liquid is not limited as long as the organomagnesium halide is stably dissolved, but is not limited to ammonium ionic liquid, imidazolium ionic liquid, phosphonium ionic liquid, pyrazolium ionic liquid, pyridinium ion. A liquid, a pyrrolidinium ionic liquid, a sulfonium ionic liquid, or the like can be used.
In the present invention, gelation means that the fluidity of a fluid liquid is lost.

2 Production of network polymer (first stage)
The first step for producing the network polymer of the present invention is to mix the linear compound represented by the formula (VI) and the cyclic compound represented by the formula (VII). The mixing conditions are not particularly limited, but are usually mixed at room temperature in an organic solvent such as dichloromethane, chloroform, tetrahydrofuran, and toluene.

(In the formula, R ¹ , R ² , R ³ and m are the same as defined in formula (I).)

(Wherein R ⁶ , R ⁷ and n are the same as defined in formula (II).)

By mixing as described above, the cyclic compound represented by the formula (VII) of 1 to (m + 1) molecules (where m + 1 corresponds to the number of N atoms in the linear compound) A compound having a pseudo-rotaxane structure represented by the unit (A) obtained by clathrating one linear compound represented by VI) can be produced. The formation of this unit (A) can be confirmed by ¹ H-NMR measurement.

In the formula, R ¹ , R ² , R ³ , R ⁶ , R ⁷ m, n and Z ⁻ are the same as defined in the formulas (I) and (II).

(Second stage)
The second step is to subject the unit (A) to olefin metathesis polymerization. The unit (A) can be subjected to a polymerization reaction after isolation if possible, but is usually represented by a linear compound represented by the formula (VI) and a formula (VII). After mixing with the cyclic compound to form the unit (A), the polymerization reaction is carried out as it is.
In addition to the olefin metathesis polymerization, the polymerization reaction can be performed by, for example, cationic polymerization, anionic polymerization, radical polymerization, coordination polymerization, ring-opening polymerization, or the like.

  The olefin metathesis polymerization reaction is performed by recombination of the double bond part of the linear compound represented by the formula (VI) and the double bond part of the cyclic compound represented by the formula (VII) by the action of the catalyst. Is a reaction that occurs. At this time, even if the double bond part of the linear compound represented by Formula (VI) may react, the double bond part of the cyclic compound represented by Formula (VII) may react. The double bond part of the linear compound represented by the formula (VI) and the double bond part of the cyclic compound represented by the formula (VII) may react. However, in order to form the network polymer of the present invention, it is necessary that at least two or more double bonds of the same unit (A) each react with a double bond of another unit (A). The catalyst is not particularly limited as long as the olefin metathesis reaction proceeds, and is preferably a Grubbs catalyst, more preferably a first generation Grubbs catalyst.

  The solvent used in the olefin metathesis polymerization reaction is not limited as long as it can dissolve the unit (A) and the catalyst used in the reaction, and is preferably a solvent used in the formation of the unit (A), such as dichloromethane, chloroform, tetrahydrofuran, Toluene and the like, more preferably dichloromethane.

  The network polymer after the olefin metathesis polymerization reaction still has a carbon-carbon double bond. A carbon-carbon double bond may be generated in both a cis form and a trans form, and the polymer of the present invention includes both. The produced carbon-carbon double bond can also be partially or completely saturated, for example, by catalytic hydrogenation reaction.

  Furthermore, further substituents can be introduced into the carbon-carbon double bond after the metathesis polymerization reaction. As an example, a Diels-Alder reaction to react with a diene compound or the like, or a pericyclic reaction such as an ene reaction can be performed. As another example, an alkenyl group or an aryl group can be introduced by performing a Heck reaction using a palladium catalyst.

(Other aspects)
Other embodiments for producing the network polymer of the present invention are described below.
The first step is to polymerize the cyclic compound represented by the formula (VII) to obtain the compound represented by the formula (VII ′). The polymerization reaction is not particularly limited as long as the compound represented by the formula (VII ′) can be obtained, but olefin metathesis polymerization is particularly preferable.

In formula, R < ⁶ >, R < ⁷ > and n are the same as the definition in Formula (II), w is an integer of 2-30, and the coupling | bond part shown with the broken line represents a double bond or a single bond.

  The compound represented by the formula (VII ') obtained by olefin metathesis polymerization still has a carbon-carbon double bond. A carbon-carbon double bond may be generated in both a cis form and a trans form, and the compound represented by the formula (VII ') includes both. The produced carbon-carbon double bond is preferably saturated by a catalytic hydrogenation reaction or the like to form a single bond.

  The second step is to mix the linear compound represented by the formula (VI) and the compound represented by the formula (VII '). The mixing conditions are not particularly limited, but are usually mixed at room temperature in an organic solvent such as dichloromethane, chloroform, tetrahydrofuran, and toluene.

By mixing as described above, a pseudo-rotaxane structure (hereinafter referred to as “unit”) in which the linear compound represented by the formula (VI) is clasped into the cyclic portion of the compound represented by the formula (VII). (B) "can also be manufactured. The formation of this unit (B) can also be confirmed by ¹ H-NMR measurement.

The third step is to subject the unit (B) to olefin metathesis polymerization. The unit (B) can be subjected to a polymerization reaction after isolation if possible. Usually, after the unit (B) is formed, the polymerization reaction is performed as it is.
In addition to the olefin metathesis polymerization, the polymerization reaction can be performed by, for example, cationic polymerization, anionic polymerization, radical polymerization, coordination polymerization, ring-opening polymerization, or the like.

(Linear compound represented by formula (VI) and cyclic compound represented by formula (VII))
As the linear compound represented by the formula (VI) and the cyclic compound represented by the formula (VII), commercially available ones can be used, and a conventionally known method such as Polymer Journal, Vol. , No. 3, (2008), 205-211.

(Production of linear compounds)
Examples of the method for synthesizing the linear compound represented by the formula (VI) include the following methods.
The polyamine moiety containing R ² and the left segment containing R ¹ are combined with a base to perform amination. After removing the protective group, the right segment containing R ³ is bonded in the same manner as the left segment to obtain the basic skeleton of the linear compound. The linear compound represented by the formula (VI) can be prepared by performing anion exchange after the hydrochloride is obtained by acting hydrochloric acid on this.

In the formula, R ¹ , R ² , R ³ and Z ⁻ have the same definition as in formula (VI), PG ¹ represents an amino-protecting group, and Q ¹ and Q ³ are the same or different and represent a leaving group. Represent.

  Specific examples of the base include lithium hydride, sodium hydride, potassium hydride, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, cesium hydrogen carbonate and the like. Can be mentioned.

  The amination reaction is preferably carried out in an aprotic polar solvent. As the aprotic polar solvent, any solvent may be used as long as the reaction proceeds. Specifically, acetonitrile, dimethylformamide, dimethylacetamide N, N-dimethylimidazolidinone, hexamethylphosphoric triamide, tetrahydrofuran and the like.

  Q is a moiety that becomes a leaving group, and examples thereof include chlorine, bromine, iodine, methanesulfonyloxy group, trifluoromethanesulfonyloxy group, benzenesulfonyloxy group, toluenesulfonyloxy group and the like.

  The amination reaction may be performed using a phase transfer catalyst. As the phase transfer catalyst, crown ether, quaternary ammonium salt or the like can be used, and specifically, 12-crown-4-ether, 15-crown-5-ether, 18-crown-6-ether, etc. Examples include crown ethers, tetraalkylammonium halides such as tetraethylammonium chloride, tetraethylammonium bromide, tetra n-butylammonium chloride, and tetra n-butylammonium bromide. These phase transfer catalysts can be appropriately selected by those skilled in the art depending on the type of the base and the type of the solvent.

In the formula, a protecting group for the amino group represented by PG ¹ can be appropriately selected by those skilled in the art, and Green & Wuts, “PROTECTIVE GROUPS in ORGANIC SYNTHESIS” 4 ^th ed. John Wiley & Sons, Inc. can be referred to. . Specifically, carbonic acid amide groups such as tert-butoxycarbonyl group and benzyloxycarbonyl group, imide groups such as phthalic acid imide, and nosyl groups such as 2-nitrobenzenesulfonyl group can be used.

Commercially available compounds may be used for the left segment containing R ¹ and the right segment containing R ³ . Moreover, it can also prepare by the method shown below from commercially available terminal unsaturated alcohol.
After protecting one of the hydroxyl groups of the diol with a protecting group PG ^2, converted into an aldehyde by oxidation of the other hydroxyl groups. By performing a Wittig reaction on this aldehyde, an olefin is introduced, and after deprotection, the hydroxyl group is converted to the leaving group Z, whereby the left segment containing R ¹ can be synthesized. In the same manner, the right segment containing R ³ can be synthesized.

In the formula, R ¹ and R ³ have the same definition as in formula (VI), PG ² represents a protecting group for a hydroxyl group, and Q ¹ and Q ³ represent the same or different and represent a leaving group.

For those used as the protecting group PG ² , Green & Wuts, “PROTECTIVE GROUPS in ORGANIC SYNTHESIS” 4 ^th ed. John Wiley & Sons, Inc. can be referred to. Specifically, acyl groups such as an acetyl group and a pivaloyl group, silyl groups such as a tert-butyldimethylsilyl group, a triisopropylsilyl group, and a triethylsilyl group can be used.

  As the method for oxidizing the hydroxyl group, any method can be used as long as it selectively oxidizes a primary alcohol to an aldehyde, and specific examples include Dess-Martin oxidation and TEMPO oxidation.

Examples of the method for converting the hydroxyl group after deprotection to the leaving group Q ¹ include a method of introducing chlorine or bromine by reacting carbon tetrachloride or carbon tetrabromide in the presence of triphenylphosphine. In addition, a method of leading to a sulfonyl ester by reacting with alkyl or aryl sulfonyl chloride in the presence of a base such as a tertiary amine can be mentioned. Moreover, the method etc. which halogenate the sulfonyl ester part by making the alkali metal salt of halogen react in polar solvents, such as acetone, etc. can be mentioned.

  Moreover, when a sulfonyl ester is used as a protecting group, the removal of the protecting group and the conversion step to the leaving group can be omitted.

A commercially available polyamine can also be used for the polyamine moiety containing R ² . Moreover, it can also prepare from commercially available diamine by the method shown below.

Amination is performed using a base with a diamine selectively protected on one side and a site having R ^2b derived from the diol. A hydroxyl group after removal of the protecting group PG ² of the hydroxyl groups converted to leaving group, with sodium azide, to introduce the azide group. By reducing the azide group, the polyamine moiety can be prepared. In this way, the polyamine chain can be extended.

In the formula, R ² has the same definition as in formula (VI), PG ¹ represents an amino-protecting group, PG ² represents a hydroxyl-protecting group, and Q ² and Q ^2b represent a leaving group.

  Specific examples of the base include lithium hydride, sodium hydride, potassium hydride, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, cesium hydrogen carbonate and the like. Can be mentioned.

  The amination is preferably carried out in an aprotic polar solvent. As the aprotic polar solvent, any solvent may be used as long as the reaction proceeds. Specifically, acetonitrile, dimethylformamide, dimethylacetamide N, N-dimethylimidazolidinone, hexamethylphosphoric triamide, tetrahydrofuran and the like.

Q ² and Q ^2b are a part that becomes a leaving group, and examples thereof include chlorine, bromine, iodine, methanesulfonyloxy group, trifluoromethanesulfonyloxy group, benzenesulfonyloxy group, and toluenesulfonyloxy group.

Wherein as a conversion method to hydroxy groups leaving groups Q ^2b after deprotection, the presence of triphenylphosphine, and a method of introducing chlorine or bromine is reacted with carbon tetrachloride or carbon tetrabromide. In addition, there is a method of reacting with a sulfonic acid halide such as toluenesulfonic acid chloride or methanesulfonic acid chloride in the presence of a base such as a tertiary amine to lead to a sulfonyl ester. Moreover, the method etc. which halogenate the sulfonyl ester part by making the alkali metal salt of halogen react in polar solvents, such as acetone, etc. can be mentioned.
Also, the basic conditions, by acting the acid chloride or toluene sulfonic acid chloride or methanesulfonic acid chloride, leads to hydroxyl to acid ester can be a leaving group Q ^2b.

  The azide group can be introduced by reacting sodium azide in an aprotic solvent. Here, as the aprotic solvent, any solvent can be used as long as the reaction proceeds, and acetone, dimethylformamide, and dimethylacetamide are preferable.

  Examples of the reduction of the azide group to an amino group include a reduction method using a phosphine such as triphenylphosphine, and a reduction method by hydrogenation using a palladium catalyst or the like. In the method of reduction using phosphine, examples of the reaction solvent include ether solvents such as diethyl ether, dioxane, and tetrahydrofuran to which water is added. In the reduction by hydrogenation, any solvent may be used as long as the reaction proceeds, but a polar solvent such as methanol or ethyl acetate is preferable from the viewpoint of increasing the reactivity.

By repeating the reaction, a desired polyamine moiety containing R ² can be prepared.

3. Neutralization of network polymer The network polymer after neutralization of the network polymer of the present invention (hereinafter also referred to as “network polymer after neutralization”) is obtained by reacting the above-described network polymer with an electrophile. The —N ⁺ H ₂ — group in the unit represented by (I) is converted to a —NR ⁴ — group or —NR ⁵ — group (R ⁴ or R ⁵ represents a residue derived from an electrophile). Can be obtained as a unit represented by the formula (I ′).

  In the network polymer after neutralization obtained in this way, the interaction between the linear compound and the cyclic compound is weakened at the cross-linked site of the rotaxane structure in the polymer, the mobility of the network polymer is increased, and the ion mobility is improved. . The effect of such neutralization of the network polymer is also observed in other types of network polymers developed by the inventors, as described in WO2013 / 99224.

As the residue derived from the electrophile represented by R ⁴ or R ⁵ , the —N ⁺ H ₂ — group in the unit represented by the formula (I) is changed to —NR ⁴ — group or —NR ⁵ — group. As long as it can be converted, it is not particularly limited, and examples thereof include a linear or branched alkyl group, a linear or branched alkenyl group, an arylalkyl group, and an acyl group.

  Specific examples of the linear or branched alkyl group include methyl group, ethyl group, n-propyl group, i-propyl group, cyclopropyl group, n-butyl group, sec-butyl group, i- Examples thereof include a butyl group, a tert-butyl group, a cyclobutyl group, a pentyl group, a neopentyl group, an amyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and an undecyl group.

  Specific examples of the linear or branched alkenyl group include vinyl, allyl, methacryl, crotonyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, octenyl. Group, nonenyl group, decenyl group, undecenyl group and the like.

By the residue derived from the electrophile represented by R ⁴ or R ⁵ , to the —NR ₄ — group or —NR ₅ — group of the —N ⁺ H ₂ — group in the unit represented by the formula (I) the method of transformation is not particularly limited, for example, using a base -N + ^H 2 _- after converting the group into -NH-, cause nitrogen anion with metal hydride, R 4 ^Y or R ⁵ The method of making it react with the electrophile represented by Y is mentioned. At this time, the reactivity between the nitrogen anion and the nucleophile may be increased by adding a metal iodide or the like.

The leaving group Y of the electrophile represented by R ⁴ Y or R ⁵ Y is a group capable of converting a —N ⁺ H ₂ — group into a —NR ⁴ — group or a —NR ⁵ — group. Examples thereof include, but are not limited to, halogen such as chlorine, bromine and iodine, and sulfonyloxy such as p-toluenesulfonyloxy, benzenesulfonyloxy, methanesulfonyloxy and trifluoromethanesulfonyloxy.

The base used at this time may be either an inorganic base or an organic base, but an organic base is preferable and a tertiary amine is preferable. More specifically, triethylamine, tri-n-butylamine, diazabicycloundecene (1,8-diazabicyclo [5.4.0] undec-7-ene) and the like can be mentioned.
Examples of the metal hydride include sodium hydride, lithium hydride, and potassium hydride, and oily sodium hydride is preferable because of easy handling.
The reaction solvent is preferably an aprotic polar solvent, and examples thereof include tetrahydrofuran, N, N-dimethylformamide, hexamethylphosphoric triamide and the like.

In addition, as a method for converting an —N ⁺ H ₂ — group to an —NR ₄ — group or —NR ₅ — group by a residue derived from an electrophile represented by R ⁴ or R ⁵ , for example, a base is used. After using the -N ⁺ H ₂ -group in the repeating unit derived from formula (I) to convert to -NH-, an amide can be obtained by introducing an acyl group onto nitrogen. Moreover, the method of reducing the said amide and converting this into a corresponding alkyl group is also mentioned.

  The base used at this time may be either an inorganic base or an organic base, but an organic base is preferable and a tertiary amine is preferable. More specifically, triethylamine, tri-n-butylamine, diazabicycloundecene (1,8-diazabicyclo [5.4.0] undec-7-ene) and the like can be mentioned.

  Examples of the acylating agent include acid halides, acid anhydrides, mixed acid anhydrides, and the like, and acid halides are preferable. The reaction solvent is not particularly limited as long as it is a reaction solvent having no active hydrogen, but preferred solvents include tetrahydrofuran, toluene, dichloromethane and the like, and dichloromethane is preferred.

The amide reducing agent is not particularly limited as long as it can be converted into a residue derived from the electrophile represented by R ⁴ or R ⁵ , but lithium aluminum hydride, bis (2-methoxyethoxy) hydride, and the like. ) Aluminum hydride reducing agents such as aluminum and diisobutylaluminum hydride, and boron hydride reducing agents such as sodium borohydride, lithium borohydride, sodium cyanoborohydride, lithium triethylborohydride, and diborane. . The reaction solvent can be appropriately selected and used by those skilled in the art depending on the type of the reducing agent.

The amount of the electrophile used is preferably 1.0 molar equivalent or more with respect to the —N ⁺ H ₂ — group in the unit represented by formula (I), and 1.0 to 100.0 molar equivalent is used. It is more preferable. -N ⁺ H ₂ - is preferably to be converted based on only a part -NR ⁴ - - groups all -NR ⁴ - group or a -NR ⁵ group, or -NR ⁵ - be converted polymer network based on Are encompassed by the present invention. That is, the conversion rate of the —N ⁺ H ₂ — group to the —NR ⁴ — group or —NR ⁵ — group may be 10% or more, preferably 30% or more, more preferably 50% or more. . It can be confirmed by IR measurement that at least a part of the —N ⁺ H ₂ — group is converted to a —NR ⁴ — group or a —NR ⁵ — group.

4 Polymer Gel Electrolyte The polymer gel electrolyte of the present invention can be obtained by mixing the network polymer and / or the neutralized network polymer and an electrolyte solution.
Since the network polymer and / or the network polymer after neutralization has gelation ability with respect to various solvents, a polymer gel electrolyte is formed by containing the network polymer and the network polymer after neutralization and an electrolyte solution. To do.

  Particularly, in the polymer gel electrolyte of the present invention, since the network polymer of the present invention and the network polymer after neutralization are chemically stable, a solution of organic magnesium halide such as Grignard reagent can be used as the non-aqueous electrolyte solution. it can. The halogenated organomagnesium compound is not limited to these, but a compound represented by the following formula (M) can be used.

  In the formula, R is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, substituted or non-substituted A substituted C3-C6 cyclic alkyl group, a substituted or unsubstituted thiophene group, a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group is represented, and X represents Cl, Br, or I. In the compound represented by the formula (M), R may have one or more sites represented by Mg—X.

  Examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, and 1-methylbutyl. Group, 2-methylbutyl group, 3-methylbutyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, 3-pentyl group, n-hexyl group, 1-methylpentyl Group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl Group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, 3,3-dimethylbutan-2-yl group, 2,3-dimethylbutan-2-yl group, 3-hexyl group, 2-ethylpen A til group, 2-methylpentan-3-yl group, heptyl group, octyl group, nonyl group, decyl group and the like can be mentioned.

  Examples of the alkenyl group having 2 to 10 carbon atoms include vinyl group, 1-propenyl group, allyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1,3-butanedienyl group, 1-ethylvinyl group, 1-methyl-1-propenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, pentenyl group, pentadienyl group, hexenyl group, hexadienyl group, hexatrienyl group, heptenyl Group, heptadienyl group, heptatrienyl group, octenyl group, octadienyl group, octatrienyl group, octatetraenyl group, nonenyl group, nonadienyl group, nonatrienyl group, nonatetraenyl group, decenyl group, decadienyl group, decatrienyl group, decatetraenyl group, A decapentaenyl group is mentioned.

  Examples of the alkynyl group having 2 to 10 carbon atoms include ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1,3-butanediynyl group, and 1-methyl. 2-propynyl group, pentynyl group, pentadiynyl group, hexynyl group, hexadiynyl group, hexatriinyl group, heptynyl group, heptadiynyl group, heptatriinyl group, octynyl group, octadiynyl group, octatriinyl group, octatetrinyl group, noninyl Group, nonadiynyl group, nonatriynyl group, nonatetrinyl group, decynyl group, decadiynyl group, decatriynyl group, decaterinyl group, decapentynyl group and the like.

  Examples of the cyclic alkyl group having 3 to 6 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

  Examples of the substituent for the alkyl group, alkenyl group, alkynyl group, cyclic alkyl group, thiophenyl group, phenyl group, and naphthyl group include fluorine, chlorine, bromine, iodine, alkyl group, alkenyl group, alkynyl group, cyclic alkyl group, alkoxy Group, alkenyloxy group, alkynyloxy group, cyclic alkoxy group, aryl group, aryloxy group, nitro group and the like.

  Specific examples of the compound represented by the formula (M) include methyl magnesium chloride, methyl magnesium bromide, methyl magnesium iodide, ethyl magnesium chloride, ethyl magnesium bromide, ethyl magnesium iodide, butyl chloride. Magnesium, butylmagnesium bromide, butylmagnesium iodide, benzylmagnesium chloride, benzylmagnesium bromide, benzylmagnesium iodide, and the like. More preferred are methylmagnesium chloride, methylmagnesium bromide, ethylmagnesium chloride, bromide. Examples include ethyl magnesium, butyl magnesium chloride, butyl magnesium bromide, benzyl magnesium chloride, and benzyl magnesium bromide, and more preferably methyl magnesium bromide, ethyl magnesium bromide, and butyl bromide. Magnesium and the like, most preferably include methyl magnesium bromide or ethyl magnesium bromide.

  The organic magnesium halide represented by the formula (M) can be prepared from a compound represented by R—X and magnesium by a conventional method. Where R is as defined above. When preparing a compound represented by the formula (M), which is difficult to prepare by a conventional method, by reacting the magnesium activated by the Reike method with the compound represented by the R—X, the formula (M) The represented compounds can also be prepared.

  The solvent of the electrolyte solution is not limited as long as the organic magnesium halide is stably dissolved. Alkane organic solvents such as pentane, hexane, and heptane, and aromatic organic solvents such as benzene and toluene. And ether-based organic solvents such as diethyl ether, dibutyl ether, methyl tert-butyl ether, tetrahydropyran, and dioxane. In addition to the organic solvent, an ionic liquid that is excellent in safety, has high ionic conductivity, and can exhibit good reversibility of magnesium dissolution and precipitation can be used.

  The ionic liquid is not limited as long as the organomagnesium halide is stably dissolved, but is not limited to ammonium ionic liquid, imidazolium ionic liquid, phosphonium ionic liquid, pyrazolium ionic liquid, pyridinium ion. A liquid, a pyrrolidinium ionic liquid, a sulfonium ionic liquid, or the like can be used. Among them, preferred are ammonium-based ionic liquids, imidazolium-based ionic liquids, and pyrrolidinium-based ionic liquids, and most preferred are ammonium-based ionic liquids.

  Specific examples of the ammonium-based ionic liquid include diethylmethylmethoxyethylammonium bis (trifluoromethane) sulfonimide salt, methyltri-n-octylammonium bis (trifluoromethane) sulfonimide salt, and ethyldimethylpropylammonium bis (trifluoromethane). Sulfonimide salt, tetrabutylammonium bis (trifluoromethane) sulfonimide salt, benzyltrimethylammonium tribromide, tetraoctylammonium chloride, and the like, more preferably diethylmethylmethoxyethylammonium bis (trifluoromethane) sulfonimide salt, Methyltri-n-octylammonium bis (trifluoromethane) sulfonimide salt, ethyldimethylpropylammonium Bis (trifluoromethane) sulfonimide salt, tetrabutylammonium bis (trifluoromethane) sulfonimide salt, and more preferably diethylmethylmethoxyethylammonium bis (trifluoromethane) sulfonimide salt, methyltri-n-octylammonium bis ( Trifluoromethane) sulfonimide salt, and most preferably, diethylmethylmethoxyethylammonium bis (trifluoromethane) sulfonimide salt.

In addition to the electrolyte using the organomagnesium halide, a conventionally known inorganic ion salt used in a non-aqueous electrolyte solution can be used as the electrolyte. For example, lithium chloride (LiCl), lithium perchlorate ( LiClO ₄ ), lithium hexafluoroarsenate (LiAsF ₆ ), lithium hexafluorophosphate (LiPF ₆ ), lithium tetrafluoroborate (LiBF ₄ ), lithium tetraphenylborate (LiB (C ₆ H ₅ ) ₄ ), Lithium methanesulfonate (LiCH ₃ SO ₃ ), lithium trifluoromethanesulfonate (LiCF ₃ SO ₃ ), lithium bis (pentafluoroethanesulfonyl) imide (Li (C ₂ F ₅ SO ₂ ) ₂ N), bis ( trifluoromethanesulfonyl) imide lithium _{(Li (CF 3 SO 2)} 2 N) Tris (trifluoromethanesulfonyl) methyl lithium _{(LiC (CF 3 SO 2)} 3), it is possible to use lithium bromide (LiBr), may be used by mixing two or more of these.

  As a solvent used for an electrolyte other than the electrolyte using the organomagnesium halide, a conventionally known solvent used for a nonaqueous electrolyte solution can be used. For example, 4-fluoro-1,3-dioxolane-2- ON, ethylene carbonate, propylene carbonate, vinylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, γ-butyrolactone, γ-valerolactone, 1,2-dimethoxyethane, 1,2-diethoxyethane, tetrahydrofuran, 2-methyl Tetrahydrofuran, 1,3-dioxolane, 4-methyl-1,3-dioxolane, diethyl ether, methyl acetate, methyl propionate, ethyl propionate, propyl propionate, acetonitrile, propionitrile, anisole, Acetate, butyrate, glutaronitrile, adiponitrile, methoxyacetonitrile, 3-methoxypropionitrile, N, N-dimethylformamide, N-methylpyrrolidinone, N-methyloxazolidinone, nitromethane, nitroethane, sulfolane, methylsulfolane, dimethylsulfoxide , Trimethyl phosphate, triethyl phosphate, ethylene sulfide, bistrifluoromethylsulfonylimide, trimethylhexylammonium, and the like can be used, and a mixture of two or more of these can also be used.

  Among the electrolyte solutions, an electrolyte solution in which ethyl magnesium bromide is dissolved in a solvent containing diethylmethylmethoxyethylammonium bis (trifluoromethane) sulfonimide salt is preferable.

  The ratio of the solute and the solvent in the electrolytic solution may be any ratio as long as the solute is dissolved in the solvent, but the solute: solvent is a substance amount ratio of 0.1: 10 to 10: 0.1, More preferably, it is 1:10 to 10: 1, more preferably 1: 5 to 5: 1, and most preferably 1: 2 to 2: 1.

  The polymer gel electrolyte of the present invention can be obtained by gelling an electrolyte solution with a network polymer. Specifically, a production method in which a predetermined amount of network polymer is immersed in a predetermined amount of electrolyte solution is exemplified. Usually, since the organomagnesium halide reacts with moisture and oxygen in the air to form a non-moving substance, the above operation is preferably performed under an inert gas.

(Non-aqueous electrolyte secondary battery)
The polymer gel electrolyte can be used as a non-aqueous electrolyte secondary battery such as a magnesium secondary battery or a lithium ion secondary battery.

  The non-aqueous electrolyte secondary battery of the present invention has a conventionally known configuration except that the polymer gel electrolyte is used.

  For example, the positive electrode is not particularly limited as long as it absorbs positive ions or discharges negative ions during discharge, and has a high conductivity such as metal oxide, polyacetylene, polyaniline, polypyrrole, polythiophene, and polyparaphenylene. Conventionally known materials such as molecules, derivatives thereof, and disulfide compounds can be used as positive electrode materials for secondary batteries.

  The negative electrode is not particularly limited as long as it is a material capable of occluding and releasing cations. Crystalline carbon such as graphitized carbon obtained by heat treatment of natural graphite, coal / petroleum pitch, etc., coal, petroleum Conventionally known negative electrode active materials for secondary batteries such as amorphous carbon obtained by heat treatment of pitch coke, acetylene pitch coke, and lithium alloys such as metallic lithium and AlLi can be used.

  Furthermore, when forming an electrode, these electrode active materials can be mixed with an appropriate binder or functional material to form an electrode layer. As the binder, a halogen-containing polymer such as polyvinylidene fluoride is used, and as the functional material, a conductive polymer such as acetylene black, polypyrrole, or polyaniline for ensuring electronic conductivity, ion conductivity, or the like. For example, a polymer electrolyte, a composite thereof, and the like.

  The nonaqueous electrolyte secondary battery of the present invention can be obtained by assembling a battery using the polymer gel electrolyte, the positive electrode and the negative electrode. There is no restriction | limiting in particular about another component and structure, The various component and structure employ | adopted by the conventionally well-known nonaqueous electrolyte secondary battery are applicable.

  For example, a polymer gel electrolyte can be supported on the separator substrate. As a separator base material, what is normally used as a separator base material for nonaqueous electrolyte secondary batteries can be used. For example, polyethylene nonwoven fabric, polypropylene nonwoven fabric, polyester nonwoven fabric, PTFE porous film, kraft paper, rayon fiber / sisal fiber mixed paper, manila hemp sheet, glass fiber sheet, cellulosic electrolytic paper, paper made of rayon fiber, cellulose and glass fiber Can be used, or a combination of these can be used to form a plurality of layers.

  Moreover, in the nonaqueous electrolyte secondary battery of this invention, there is no restriction | limiting in particular also about the shape. For example, any of a coin shape, a button shape, a sheet shape, a laminated shape, a cylindrical shape, a flat shape, a square shape, a large size used for an electric vehicle, etc. may be used. The polymer gel electrolyte of the present invention has a significantly lower content of the electrolyte solution than the conventional secondary battery, so that the effects of the present invention are remarkable in terms of safety and manufacturing cost, especially when manufacturing a large battery. Appear in

  Hereinafter, the present invention will be described in more detail with reference to Examples, but the technical scope of the present invention is not limited thereto.

(1) Synthesis of linear compound The linear compound was synthesized by the following procedure.
(I) Synthesis of 1,2-bis (10-undecenoylaminoethoxy) ethane

  To a THF solution of 2,2 ′-(ethylenedioxy) bis (ethylamine) (3.00 g, 0.0202 mol) and triethylamine (7.04 ml, 0.0505 mmol), 10-undecenoyl chloride (9.00 g, 0 0.044 mol) in THF was added dropwise and stirred at room temperature for 17 hours. After the reaction, 5 ml of an aqueous sodium hydrogen carbonate solution was added, diluted with ethyl acetate, and washed with water three times. The washed organic layer was dried over anhydrous magnesium sulfate and concentrated. The concentrate was further washed with hexane to obtain 1,2-bis (10-undecenoylaminoethoxy) ethane white powder (yield 7.07 g, 73% yield).

(Ii) Synthesis of 1,2-bis (N- (10-undecen-1-yl) aminoethoxy) ethane

  A dehydrated THF solution of 1,2-bis (N- (10-undecen-1-yl) aminoethoxy) ethane (3.00 g, 6.24 mmol) was added dropwise to a THF suspension of lithium aluminum hydride for 35 hours. Refluxed. After cooling with ice, the reaction was stopped by adding ethyl acetate and distilled water, followed by filtration under reduced pressure. The filtrate was dried to obtain 1,2-bis (N- (10-undecen-1-yl) aminoethoxy) ethane (yield 2.81 g, yield 99%) as a yellow transparent viscous liquid.

(Iii) 1,2-bis (N- (10-undecen-1-yl) aminoethoxy) ethane Synthesis of dihexafluorophosphoric acid

A methanol solution of 1,2-bis (N- (10-undecen-1-yl) aminoethoxy) ethane (2.81 g, 6.21 mmol) was acidified with a 3N HCl aqueous solution. After removing methanol by concentration, the aqueous layer was extracted with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate and concentrated to give a white solid. The white solid was dissolved in methanol and added dropwise to a saturated aqueous hexafluorophosphoric acid solution. The mixture was diluted with water, extracted with dichloromethane, dried and concentrated. The concentrate was washed with hexane / ether = 2/1 and 1,2-bis (N- (10-undecen-1-yl) aminoethoxy) ethane dihexafluorophosphoric acid white solid material (yield 3.77 g, Yield 82%). The ¹ H-NMR spectrum of this compound is shown in FIG. 1, and the IR spectrum is shown in FIG.

(2) Synthesis of cyclic compound The linear compound (iv) was synthesized by the following procedure.
(I) Synthesis of p-toluenesulfonic acid 10-undecenyl ester

To a THF solution of 10-undecen-1-ol (8 g, 0.0470 mol), dimethylaminopyridine (DMAP) (0.12 g, 9.40 × 10 ⁻⁴ mol), triethylamine (13.5 ml, 0.0969 mol). A THF solution of p-toluenesulfonyl chloride (TsCl) (13.4 g, 0.0705 mol) was added dropwise, and the mixture was stirred at room temperature for 71 hours. The reaction was stopped by adding a saturated aqueous solution of sodium bicarbonate, diluted with water, and extracted with ethyl acetate. The extract was dried over anhydrous magnesium sulfate, concentrated, purified by column chromatography (silica gel, hexane: ethyl acetate = 15: 1 to 9: 1), and p-toluenesulfonic acid 10-undecenyl ester (yield 14.5 g, yield). 95%) was obtained as a colorless and transparent liquid.

(Ii) Synthesis of bis (formylbenzo) -24-crown-8-ether

  Dibenzo-24-crown-8-ether (DB24C8) (0.50 g, 1.14 mmol), hexamethylenetetramine (0.799 g, 5.70 mmol) were added with trifluoroacetic acid (2 ml), and the mixture was heated in an oil bath at 60 ° C. Heated for 24 hours. Distilled water (5 ml) was then added, extracted with dichloromethane (100 ml × 3), dried over anhydrous magnesium sulfate and concentrated. Purification by silica gel column chromatography (dichloromethane: methanol = 10: 1) gave bis (formylbenzo) -24-crown-8-ether (yield 0.474, yield 82%) as yellowish white crystals.

(Iii) Synthesis of bis (hydroxymethylbenzo) -24-crown-8-ether

  Bis (formylbenzo) -24-crown-8-ether (0.47 g, 0.94 mmol) was dissolved in THF (30 ml). Further, sodium borohydride (0.80 g, 2.81 mmol) was added and refluxed for 24 hours. Thereafter, THF was removed by concentration. The mixture was extracted 3 times with dichloromethane (100 ml), dried over anhydrous magnesium sulfate and concentrated. Yellowish white crystals of bis (hydroxymethylbenzo) -24-crown-8-ether (yield 0.39 g, yield 82%) were obtained.

(Iv) Synthesis of bis (10-undecenyloxymethylbenzo) -24-crown-8-ether

A dehydrated THF solution of 1.00 g (1.97 mmol) of bis (hydroxymethylbenzo) -24-crown-8-ether was added to a suspension of sodium hydride (0.136 g, 5.91 mmol) in THF under ice cooling. It was. A THF solution of 1.92 g (5.91 mmol) of p-toluenesulfonic acid 10-undecenyl ester was slowly added dropwise to the solution. After reacting under reflux conditions for 65 hours, an aqueous sodium hydrogen carbonate solution was added at room temperature, and the mixture was extracted with dichloromethane. The extract was dried over anhydrous magnesium sulfate and concentrated. Thereafter, the product was purified by silica gel column chromatography (dichloromethane: ethyl acetate = 9: 1 → 1: 1). Bis (10-undecenyloxymethylbenzo) -24-crown-8-ether (white solid) was obtained (yield 0.700 g, yield 43.7%). The ¹ H-NMR spectrum of this compound is shown in FIG.

Synthesis of network polymer gel 20 mg (2.38 × 10 ⁻⁵ mol) of bis (undecylenyloxymethylbenzo) -24-crown-8-ether and 1,2-bis (N- (10-undecen-1-yl) ) Aminoethoxy) ethane Dihexafluorophosphoric acid 8.9 mg (1.19 × 10 ⁻⁵ mol) and benzylidenebis (tricyclohexylphosphine) dichlororuthenium 1.5 mg (1.79 × 10 ⁻⁶ mol) in dichloromethane solution It apply | coated to the glass substrate, and after natural drying, it heated at 50 degreeC for 23 hours. After the reaction, ethyl vinyl ether was added as a terminator, washed with methanol, ethyl acetate and acetone and dried to obtain a brown network polymer. The IR spectrum of the obtained network polymer is shown in FIG.
The glass transition temperature of this network polymer was −18.4 ° C.
The membrane (0.0110 g) was immersed in 5 ml of acetonitrile in a test tube, 1 mL of triethylamine and 0.5 mL of acetic anhydride were added, and the mixture was stirred in an oil bath at 40 ° C. for 24 hours. After the reaction, the membrane was washed with methanol and vacuum dried.

Neutralization of network polymer gel The network polymer (0.0110 g) synthesized in Example 1 was immersed in acetonitrile (5 ml), triethylamine (1 ml) and acetic anhydride (0.5 ml) were added, and the mixture was stirred at 40 ° C for 24 hours. . After the reaction, the membrane was washed with methanol and vacuum dried.
The glass transition temperature of this network polymer was −39.1 ° C.

Network Polymer Film Stability Test The network polymer synthesized in Example 1 was immersed in a 1M tetrahydrofuran solution of ethylmagnesium bromide in a glove box under an argon atmosphere at room temperature. As shown in FIG. 5, the network polymer of the present invention was confirmed to be stable without being observed to be broken or deteriorated even after being immersed for one month. On the other hand, the network polymer having a conventional rotaxane structure having an ester bond started to deteriorate in only 10 minutes under the same conditions, and the deterioration was remarkable after 15 minutes, and the film structure could not be maintained.

Measurement of ionic conductivity of electrolyte using network polymer The network polymer synthesized in Example 1 was immersed in an electrolyte solution composed of a 1M lithium hexafluorophosphate ethylene carbonate-dimethyl carbonate solution, and a polymer gel electrolyte was obtained. Prepared. Table 1 shows the measurement results of the swelling degree and ionic conductivity of the prepared electrolyte.

  As shown in Table 1, the polymer gel electrolyte prepared using the network polymer of the present invention has a low degree of swelling and high ion conductivity despite a small amount of electrolytic solution retained.

  The network polymer obtained in the present invention exhibits high ionic conductivity despite the small amount of electrolyte solution retained. Therefore, the problems of the liquid leakage and the manufacturing cost of the conventional nonaqueous electrolyte secondary battery can be solved, and it can be a safer and cheaper material for the nonaqueous electrolyte secondary battery.

Claims (10)

Formula (I)
^(Wherein, R 1, ^{R 2} and ^{R 3} are the same or different, -O- and have rather good also, a linear or branched 1 to 15 carbon atoms which may be substituted with an alkoxy group represents an alkylene group, m represents an integer of 1 to 10, when m is 2 or more, each R ² may be the same or different, Z ^- represents a counter anion, a plurality of Z ^- May be the same or different from each other), or the following formula (I ′)
(In the formula, R ¹ , R ² , R ³ , and m are the same as defined in formula (I), and R ⁴ and R ⁵ are the same or different and represent a residue derived from an electrophile. Per unit of linear unit represented by the following formula (II)
(Wherein, R ⁶ and R ⁷ are the same or different, rather it may also have a -O-, linear or branched alkylene group having 1 to 15 carbon atoms which may be substituted with an alkoxy group N represents an integer of 3 or 4. 1 to (m + 1) units (where m is synonymous with m in formula (I)) are clasped in a skewered manner. A network polymer having the unit (A). 2. The network polymer according to claim 1, wherein the network polymer has 2 to 1000 units (A). The cyclic unit represented by the formula (II) is represented by the following formula (III)
(Wherein, R ⁶ and R ⁷ are the same or different, rather it may also have a -O-, linear or branched alkylene group having 1 to 15 carbon atoms which may be substituted with an alkoxy group And the dotted line part is a unit represented by the following: 3) or 3rd position of the benzene ring. The unit represented by the formula (III) is the following formula (IV)
(In the formula, n3 and n4 are the same or different and each represents an integer of 1 to 14, and the dotted line portion indicates that it is bonded to either the 3-position or 4-position of the benzene ring). The network polymer according to claim 3, which is a unit represented. The linear unit represented by the formula (I) is represented by the following formula (V)
(Wherein R ¹ , R ² , R ³ , and Z ⁻ are the same as defined in formula (I)). The network polymer described. First step: Formula (VI)
^(Wherein, R 1, ^{R 2} and ^{R 3} are the same or different, -O- and have rather good also, a linear or branched 1 to 15 carbon atoms which may be substituted with an alkoxy group represents an alkylene group, m represents an integer of 1 to 10, when m is 2 or more, each R ² may be the same or different, Z ^- represents a counter anion, a plurality of Z ^- May be the same or different, and a linear compound represented by the following formula (VII):
(Wherein, R ⁶ and R ⁷ are the same or different, rather it may also have a -O-, linear or branched alkylene group having 1 to 15 carbon atoms which may be substituted with an alkoxy group And n represents an integer of 3 or 4.) and a cyclic compound represented by
For one molecule of the linear compound represented by the formula (VI), 1 to (m + 1) molecules of the cyclic compound represented by the formula (VII) (where m is the same as m in the formula (VI)). A compound (A ′) having a structure formed by inclusion in a skewered manner, and
2nd process: The manufacturing method of the network polymer in any one of Claims 1-5 which has the process of carrying out the olefin metathesis polymerization of the said compound (A '). After the first step or the second step,
Third step: reacting the product with an electrophile,
Formula (I)
^(Wherein, R 1, ^{R 2} and ^{R 3} are the same or different, - it may also have O- a rather straight-chain or branched 1 to 15 carbon atoms which may be substituted with an alkoxy group represents an alkylene group, m represents an integer of 1 to 10, when m is 2 or more, each R ² may be the same or different, and Z ^- represents a counter anion, a plurality of Z ^- is, respectively The units represented by formula (I ′) may be the same or different.
(In the formula, R ¹ , R ² , R ³ , and m are the same as defined in formula (I), and R ⁴ and R ⁵ are the same or different and represent a residue derived from an electrophile. The method for producing a network polymer according to claim 6, further comprising a step of converting to a unit represented by: The polymer gel electrolyte characterized by containing the network polymer in any one of Claims 1-5 in the electrolyte solution containing halogenated organomagnesium . 9. The polymer gel electrolyte according to claim 8, wherein the electrolytic solution is a solution of ethyl magnesium bromide in diethylmethylmethoxyethylammonium bis (trifluoromethane) sulfonimide. A secondary battery using the polymer gel electrolyte according to claim 8.