JP2016162543A - Polymer electrolyte containing rotaxane network polymer and magnesium secondary battery using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an electrolyte for use in a magnesium secondary battery, with which magnesium ions can be repeatedly dissolved/precipitated between an electrolytic solution and a negative electrode.SOLUTION: In a magnesium battery using a polymer gel electrolyte containing (1) a rotaxane network polymer and (2) an electrolytic solution containing a magnesium salt, magnesium ions can be repeatedly dissolved/precipitated between the polymer gel electrolyte and metal magnesium of a negative electrode.SELECTED DRAWING: None

Description

  The present invention relates to a polymer gel electrolyte containing an electrolyte solution containing a rotaxane network polymer and a magnesium salt, and also relates to a magnesium secondary battery using the electrolyte.

  Magnesium secondary batteries are expected as next-generation secondary batteries that exceed lithium ion secondary batteries because of their high theoretical capacity (2290 mAh / g) and abundant resources, as well as high safety. However, since magnesium ions are divalent ions, the interaction with the positive electrode material (electrostatic attractive force with anions) is stronger than that of monovalent lithium ions, and the electrode reaction (magnesium insertion and desorption reaction rate) is higher. There are problems such as a very slow point and an oxide film of magnesium formed at room temperature on the negative electrode side at the time of charge / discharge, making it difficult for a reversible dissolution and precipitation reaction between the electrolyte and magnesium metal to occur. Therefore, with respect to the former point, there is a need for an electrolyte solution capable of repeated dissolution and precipitation with respect to the latter point of the positive electrode material that has a fast insertion / desorption reaction.

Regarding a magnesium secondary battery, a magnesium secondary battery using MgFeSiO _{4 as} a positive electrode, magnesium as a negative electrode, and Mg (TFSA) ₂ / Triglyme as an electrolyte has been reported (Patent Document 1). However, the magnesium secondary battery reported in Patent Document 1 has an operating temperature as high as 100 ° C. When the operating temperature is high, there is a problem that the battery is deteriorated and the life of the battery is shortened.

  On the other hand, the applicant of the present application is that in a lithium secondary ion battery, the polymer gel electrolyte obtained from the clathrate type network polymer (rotaxane network polymer) and the electrolyte solution reduces the amount of the electrolyte solution to about one fifth. However, it has been reported that high ionic conductivity is exhibited (Patent Document 1). The rotaxane network polymer penetrates the opening of a cyclic molecule (rotator) in a straight line with a linear molecule (axis: axis) to include the cyclic molecule with the linear molecule, and the cyclic molecule is detached. It is a polymer in which blocking groups are arranged at both ends of a linear molecule so that there is no possibility.

  However, it is not known that an electrolyte containing a rotaxane network polymer can be used for a magnesium secondary battery.

International Publication No. 2013/099224 Pamphlet

"High energy density rechargeable magnesium battery using earth-abundant and non-toxic elements" Scientific Reports 4, Article number: 5622 Published 11 July 2014

  The present invention has been made in view of such circumstances, and an object thereof is to obtain an electrolyte that can be used for a magnesium secondary battery, in which magnesium can be repeatedly dissolved and precipitated with an electrolyte in a negative electrode. To do.

  As a result of intensive studies to solve the above problems, the inventor of the present invention uses a clathrate type network polymer (rotaxane network polymer) and a magnesium salt solution for a magnesium secondary battery. In the meantime, it was found that magnesium ions could be repeatedly dissolved and precipitated, and the present invention was completed. In addition, it has been clarified that a magnesium secondary battery using an electrolyte containing an inclusion type network polymer (rotaxane network polymer) and a magnesium salt solution operates at room temperature. In particular, when an organic sulfur material is used for the positive electrode, an excellent magnesium secondary battery capable of stably charging and discharging with a large capacity can be obtained.

That is, the present invention relates to the following.
[1] (1) Formula (I)
Wherein R ¹ and R ² are the same or different and may have —O—, —CO—, —COO—, or —CONH—, saturated or partially unsaturated, linear or branched In the cyclic part of the partial structure represented by the chain, a hydrocarbon group having 1 to 15 carbon atoms, n1 represents an integer of 3 or 4. n2 represents an integer of 1 to 30.
Formula (II)
Wherein R ³ and R ⁴ are the same or different and may have —O—, —CO—, —COO— or —CONH—, saturated or partially unsaturated, linear or branched Represents a hydrocarbon group having 1 to 15 carbon atoms in the chain, and Z ⁻ represents a counter anion.), Or Formula (II ′)
(Wherein R ³ and R ⁴ are the same as defined in formula (II), and R ⁵ represents a residue derived from an electrophile), and the partial structure represented by skewering is included. A polymer comprising a rotaxane network polymer having a unit (A) or an electrolyte solution containing the unit (A) and a rotaxane network polymer having a unit (B) derived from a radical polymerizable monomer and (2) a magnesium salt Gel electrolyte.
[2] (1) The unit (A) of the rotaxane network polymer is
Formula (III)
(In the formula, m is an integer of 1 to 13, and the dotted line part indicates that it is bonded to either the 3-position or the 4-position of the benzene ring. N2 represents an integer of 1 to 30). In the annular part of the partial structure
Formula (IV)
In the above [1], wherein the partial structure represented by (wherein y represents an integer of 1 to 12 and Z ⁻ represents a counter anion) is included in a skewered manner. The polymer gel electrolyte described.
[3] The polymer gel electrolyte according to the above [1] or [2], wherein the electrolyte solution containing a magnesium salt is a triethylene glycol dimethyl ether (Triglyme) solution of Mg (TFSA) ₂ .
[4] A magnesium secondary battery using the electrolyte according to any one of [1] to [3].
[5] The magnesium secondary battery as described in [4] above, wherein the positive electrode is an organic sulfur material or vanadium pentoxide, and the negative electrode is magnesium metal.
[6] The magnesium secondary battery as described in [5] above, wherein the positive electrode is a sulfur-containing polymer.

  By using the polymer gel electrolyte of the present invention for a magnesium secondary battery, charging and discharging can be repeated. Moreover, since the operating temperature of the magnesium secondary battery of this invention operate | moves at room temperature, deterioration of the battery which occurs by the operation | movement at high temperature can be prevented, and a battery with a long lifetime can be obtained. Furthermore, since the electrolyte of the magnesium secondary battery of the present invention is a gel electrolyte, it has a liquid leakage preventing effect and is safe.

It is a figure showing the structure of the magnesium secondary battery created in Example 2 which uses an organic sulfur material for a positive electrode. It is a figure showing the result of the charging / discharging measurement of the magnesium secondary battery manufactured in Example 2 which uses organic sulfur material for a positive electrode. It is a figure showing the result of the charging / discharging measurement of the magnesium secondary battery manufactured in Example 2 which uses vanadium pentoxide for a positive electrode.

(Polymer gel electrolyte)
The polymer gel electrolyte of the present invention is a polymer gel electrolyte containing an electrolyte solution containing (1) a rotaxane network polymer and (2) a magnesium salt.

(1) Rotaxane network polymer The rotaxane network polymer contained in the polymer gel electrolyte of the present invention includes a network polymer having a -N ⁺ H ₂ -group (network polymer P) and a -N ⁺ H ₂ -group in an electrophilic agent. Includes a summed network polymer (network polymer Q). Moreover, the polymer gel electrolyte of this invention can use the rotaxane network polymer as described in the international publication 2013/099224 pamphlet.

[Network polymer having -N ⁺ H ₂ -group (network polymer P)]
The network polymer before neutralization of the present invention is a unit (A) in which a partial structure represented by the following formula (II) is clasped into an annular portion of a partial structure represented by the following formula (I) (A ) Having a network polymer (hereinafter referred to as “network polymer P-1”) or a network polymer having the unit (A) and a unit (B) derived from a radical polymerizable monomer (hereinafter referred to as “network polymer P-2”). ).

In the formula, R ¹ and R ² are the same or different and may be —O—, —CO—, —COO— or —CONH—, saturated or partially unsaturated, linear or branched Of the hydrocarbon group having 1 to 15 carbon atoms, n1 represents an integer of 3 or 4, and n2 represents an integer of 1 to 30.
R ² is bonded to the 3rd or 4th position as viewed from the carbon atom to which the alkylene group having an ether bond is bonded, and may be either the 3rd or 4th position, or a mixture thereof. There may be.

In the formula, R ³ and R ⁴ are the same or different and may be —O—, —CO—, —COO— or —CONH—, saturated or partially unsaturated, linear or branched Represents a hydrocarbon group having 1 to 15 carbon atoms, and Z ⁻ represents a counter anion.

R ¹ , R ² , R ³ and R ⁴ , “saturated or partially unsaturated, linear or branched, optionally having —O—, —CO—, —COO— or —CONH— In the “chain hydrocarbon group having 1 to 15 carbon atoms”, the “saturated or partially unsaturated, linear or branched 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 Alkylene groups such as groups; ethylidene group, propylidene group, isopropylidene group, sec-butylidene group, tert-butylidene group, n-pentylidene group, n Examples thereof include alkylidene groups such as a hexylidene group, a decamethylidene group, and a pentadecamethylidene group, but a saturated or partially unsaturated linear or branched hydrocarbon group having 1 to 15 carbon atoms. Although not restricted to these, it is more preferable that it is C1-C11 from points, such as a steric hindrance.

In the partial structure represented by the formula (II), the counter anion represented by Z ⁻ is not particularly limited, but is represented by the formula (II) in the cyclic portion of the partial structure represented by the formula (I). -N ^{+ in} a unit derived from a partial structure represented by formula (II) in the rotaxane structure or rotaxane structure, which can be constructed as a rotaxane structure or a rotaxane structure in which the partial structure is included in a skewered manner A monovalent anion capable of converting an H ₂ -group into an —NR ⁵ — group (R ⁵ represents a residue derived from an electrophile) is preferred.
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. Can be 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, trifluoromethyl, Examples include fluorinated alkyl groups such as pentafluoroethyl, heptafluoropropyl and nonafluorobutyl.

The “unit (B) derived from the radically polymerizable monomer” is a structure included in the network polymer P-2, and the radically polymerizable monomer is not particularly limited as long as it is a compound having radically polymerizable properties. Is the following formula: CR ^a R ^b = CR ^c R ^d
(Wherein R ^a , R ^b and R ^c are the same or different and each represents a hydrogen atom or a halogen-substituted or unsubstituted lower alkyl, and R ^d represents an alkyl group, an alkenyl group, an alkyloxycarbonyl group, an aryl group, carbamoyl) 1 type or a mixture of 2 or more types of compounds represented by the above).

  Examples of the radical polymerizable monomer include styrene and styrene derivatives, (meth) acrylic acid and (meth) acrylic acid derivatives, (meth) acrylamide and (meth) acrylamide derivatives, (meth) acrylonitrile, isoprene, and 1,3-butadiene. , Ethylene, vinyl acetate, vinyl chloride, vinylidene chloride and the like.

  Specific examples of styrene and derivatives thereof include styrene, tert-butylstyrene, tert-butoxystyrene, hydroxystyrene, vinyltoluene, chlorostyrene, and salts thereof.

  Specific examples of (meth) acrylic acid and derivatives thereof include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and (meth) acrylic acid. Isopropyl, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, (meth) acrylic acid Cyclohexyl, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, (Meth) acrylic acid phenyl, (meth) acrylic acid toluyl, (meth) acrylic acid benzyl, (meth) acrylic 2-methoxyethyl, (meth) 3-methoxybutyl acrylate, 2-hydroxyethyl (meth) acrylate, (meth) acrylate, 2-hydroxypropyl, and (meth) polyethylene glycol acrylate. Of these, methyl (meth) acrylate and ethyl (meth) acrylate are more preferably used.

Examples of (meth) acrylamide and derivatives thereof include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nn-butyl (meth) acrylamide, N -N-alkyl (meth) acrylamides such as tert-butyl (meth) acrylamide; N, N-dialkylacrylamides such as N, N-dimethylacrylamide and the like.
Among these, methyl methacrylate, n-butyl methacrylate, 2-hydroxyethyl methacrylate, polyethylene glycol methacrylate, styrene and acrylonitrile are preferable.

In the network polymer P, the unit (A) in which the partial structure represented by the formula (II) is clasped into the annular portion of the partial structure represented by the formula (I) is a rotaxane structure. It is. Rotaxane refers to a ring in which a rod-like molecule penetrates a macrocyclic molecule and a bulky site is bonded to both ends of the shaft so that the ring cannot be removed from the shaft due to steric hindrance. The bulky part is called a stopper, cap, or 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 of the present invention has no stopper component and is constructed only from a ring and a shaft. In this sense, the unit (A) can be said to be a pseudorotaxane. However, by configuring the network, another pseudo-rotaxane unit or another pseudo-rotaxane unit bonded via a radical polymerizable monomer serves as a stopper, so the ring and the axis are not separated. Is included.

  “Network polymer P-1” contains unit (A) in its structure. The molar ratio of the partial structure represented by the formula (I) and the partial structure represented by the formula (II) is 1 to 10: 1, preferably 1 to 3: 1, more preferably 1: 1.

  “Network polymer P-2” contains unit (A) and unit (B) in its structure. The molar ratio of the partial structure represented by the formula (I) and the partial structure represented by the formula (II) is 1 to 10: 1, preferably 1 to 3: 1, more preferably 1: 1. The molar ratio of the unit (A) to the unit (B) is 1: 1 to 100, preferably 1: 2 to 50, more preferably 1: 5 to 10.

  The network polymer P is composed of 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; acetone. Ketones such as tetrahydrofuran; ethers such as diethyl ether; insoluble in solvents such as acetonitrile, N, N-dimethylformamide, ethyl acetate and the like.

  As the compound represented by the formula (I) and the compound represented by the formula (II), those which are commercially available can be used, and a conventionally known method (Polymer Journal, Vol. 40, No. 3, ( 2008), 205-211).

  The partial structure represented by the formula (I) is preferably a partial structure represented by the following formula (III).

  In formula, m is an integer of 1-13 and a dotted line part shows couple | bonding with either the 3rd-position or the 4-position of a benzene ring. n2 is the same as defined in formula (I).

  The partial structure represented by the formula (II) is preferably a partial structure represented by the following formula (IV).

In formula, y is an integer of 1-12, Z < ^- > is a counter anion, and can illustrate the same thing as Formula (II).

^[-N + _{H 2} - network polymer after neutralization of the group (Network Polymer Q)]
The network polymer after neutralization of the network polymer P of the present invention (hereinafter referred to as “network polymer Q”) is obtained by reacting the above-described network polymer P with an electrophile (R ⁵ X) to obtain the formula (II) The —N ⁺ H ₂ — group in the partial structure represented by formula (II ′) is replaced with the —NR ⁵ — group (R ⁵ represents a residue derived from an electrophile) in the partial structure represented by formula (II ′). It is a converted network polymer.

  In the network polymer Q, the interaction between the partial structure represented by the formula (I) and the partial structure represented by the formula (II ′) is weakened at the cross-linked site of the rotaxane structure in the polymer, and the mobility of the network polymer is reduced. It increases and the ion electric power improves.

In formula (II ′), R ³ and R ⁴ have the same definition as R ³ and R ⁴ in formula (II), and examples thereof are the same as those in formula (II).

As the residue derived from the electrophile represented by R ⁵ , an electrophile capable of converting the —N ⁺ H ₂ — group in the repeating unit derived from the compound represented by the formula (II) into a —NR ⁵ — group. Although it is not particularly limited as long as it is a residue derived from, for example, alkyl group, alkenyl group, arylalkyl group, alkylcarbonyl group, alkoxycarbonyl group, arylcarbonyl group, aryloxycarbonyl group, arylalkylcarbonyl group, arylalkyloxycarbonyl Group, alkylsulfonyl group, arylsulfonyl group and the like. From the viewpoint of reducing steric hindrance to the annular portion, R ⁵ preferably has about 1 to 11 carbon atoms.

  Specific examples of the alkyl group include methyl, ethyl, n-propyl, i-propyl, cyclopropyl, n-butyl, sec-butyl, i-butyl, tert-butyl, and cyclobutyl. Group, pentyl group, neopentyl group, amyl group, cyclopentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group, decanyl group, undecanyl group and the like.

  As the alkenyl group, specifically, vinyl group, allyl group, methacryl group, crotonyl group, butenyl group, pentenyl group, cyclopentenyl group, hexenyl group, cyclohexenyl group, heptenyl group, octenyl group, nonenyl group, decanenyl group, An undecanenyl group etc. are mentioned.

  Specific examples of the arylalkyl group include a benzyl group, a cinnamyl group, a hydrocinnamyl group, and a naphthalenemethyl group.

  Specific examples of the alkylcarbonyl group include formyl group, acetyl group, propionyl group, acryloyl group, propioyl group, butyryl group, isobutyryl group, methacryloyl group, crotonoyl group, isocrotonoyl group, valeryl group, isovaleryl group, and pivaloyl group. Can be mentioned.

  Specific examples of the alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, i-propoxycarbonyl group, n-butoxycarbonyl group, tert-butoxycarbonyl group, pentoxycarbonyl group, neopentyloxy A carbonyl group, an amyloxycarbonyl group, a hexyloxycarbonyl group, etc. are mentioned.

  Specific examples of the arylcarbonyl group include a benzoyl group, a toluoyl group, a naphthoyl group, a furoyl group, a thiophenecarbonyl group, a nicotinoyl group, and an isonicotinoyl group.

  Specific examples of the aryloxycarbonyl group include a phenoxycarbonyl group, a tolyloxycarbonyl group, and a naphthyloxycarbonyl group.

  Specific examples of the arylalkylcarbonyl group include benzylcarbonyl group, cinnamoyl group, hydrocinnamoyl group, naphthalenylacetyl group and the like.

  Specific examples of the arylalkyloxycarbonyl group include a benzyloxycarbonyl group and a 9H-fluoren-9-ylmethoxycarbonyl group.

  Specific examples of the alkylsulfonyl group include a methanesulfonyl group, a trifluoromethanesulfonyl group, a camphorsulfonyl group, and the like.

  Specific examples of the arylsulfonyl group include a benzenesulfonyl group, a toluenesulfonyl group, and a naphthalenesulfonyl group.

(Method for producing network polymer)
The rotaxane network polymer can be synthesized with reference to the network polymer disclosed in International Publication No. 2013/099224.

[Manufacture of network polymer P]
(First stage)
The first step for producing the network polymer P of the present invention is to mix a cyclic compound represented by the following formula (V) and a linear compound represented by the following formula (VI). The mixing conditions are not particularly limited, but they are usually mixed at room temperature in an organic solvent such as chloroform and toluene.

In formula (V), R ¹ , R ² and n1 have the same definition as R ¹ , R ² and n1 in formula (I), and examples thereof are the same as those in formula (I). X ¹ and X ² are the same or different and each represents a group that acts as a binding site during the polymerization reaction.

In formula, R < ³ >, R < ⁴ > and Z < ^- > are the same definitions as R < ³ >, R < ⁴ > and Z < ^- > in Formula (II), and can illustrate the same thing as Formula (II). X ³ and X ⁴ are the same or different and represent a group that acts as a binding site during the polymerization reaction.

The “group that acts as a binding site during the polymerization reaction” of X ^{1 to} X ⁴ is not particularly limited as long as it is a group that acts as a binding site during the polymerization reaction. For example, cationic polymerization, anionic polymerization, radical polymerization, coordination Examples thereof include polymerizable functional groups used for polymerization, metathesis polymerization, ring-opening polymerization and the like.
Specifically, acrylic group, methacryl group, styrene group, vinyl group, vinyl cyanide group, acryloyl group, methacryloyl group, acrylamide group, methacrylamide group, epoxy group, glycidyl group, glycidyl ether group, oxetanyl group, crosslinking A functional silicon group, vinyl ether group, episulfide group, ethyleneimine group, maleimide group and the like.

The “group that does not act as a binding site during the polymerization reaction” of X ¹ and X ² is a structure contained in the network polymer P-2, and X ¹ and X ² are represented by the formula (V) in the case of n2 = 1. After the compound obtained is polymerized by cationic polymerization, anionic polymerization, radical polymerization, coordination polymerization, metathesis polymerization, ring-opening polymerization or the like to produce a polymer of n2 = 2 to 30, a binding site at the time of the polymerization reaction at the end of the polymer There is no particular limitation as long as it is a functional group that does not have polymerization reactivity.
Specific examples include an alkyl group, an alkoxy group, an alkyloxycarbonyl group, and an aryl group.

  In addition, in the production of the network polymer P, a compound represented by the following formula (VII), which is a polymer, can be used instead of the compound represented by the above formula (V).

Wherein ^{(VII), R 1, R} 2, X 1, X 2 and n1 is the formula (I) and be ^{R 1, R 2, X 1} , same definition as ^{X 2} and n1 in Formula (V) The thing similar to Formula (I) and Formula (V) can be illustrated. n2 represents an integer of 2 to 30.

When the compound represented by the formula (V) and the linear compound represented by the formula (VI) are mixed, N ⁺ H in the compound represented by the formula (VI) is added to the cyclic part in the formula (V). A structure in which _two groups are included (A), that is, a rotaxane structure is formed. That is, the compound represented by the formula (V) functions as a macrocyclic compound, and the compound represented by the formula (VI) functions as a linear compound. Here, the mixing ratio of the compound represented by the formula (V) and the compound represented by the formula (VI) is 1 to 10: 1, preferably 1 to 3: 1, more preferably 1: 1 in terms of molar ratio. is there. The formation of the rotaxane complex can be confirmed by ¹ H-NMR measurement.

The compound represented by the formula (V) can be polymerized in advance. This polymer is a compound represented by the above formula (VII), and the polymerization reaction is not particularly limited as long as the compound represented by the formula (V) can be polymerized. For example, cationic polymerization, anionic polymerization, The polymerization can be carried out by radical polymerization, coordination polymerization, metathesis polymerization, ring-opening polymerization, etc., with metathesis polymerization being particularly preferred.
In addition, when the monomer represented by n2 = 1 of the cyclic compound represented by the formula (VII) and X ¹ and X ² are groups that do not act as a binding site during the polymerization reaction, the compound is used. Thus, the network polymer of the present invention can be produced.

In the metathesis polymerization reaction, when the groups X ¹ and X ² acting as a bonding site at the polymerization reaction of the cyclic compound represented by the formula (V) or the formula (VII) have a carbon-carbon double bond, by the action of the catalyst, This is a reaction in which polymerization occurs by recombination of double bond portions. The catalyst is not particularly limited as long as the metathesis reaction proceeds, but is preferably a Grubbs catalyst, more preferably a first generation Grubbs catalyst. The solvent that can be used is not limited as long as it can dissolve the compound represented by the formula (VII) in which n2 is 1 and the catalyst used in the reaction, and preferably include dichloromethane, chloroform, tetrahydrofuran, toluene, and the like. More preferably, it is dichloromethane.

In the compound represented by the formula (VII) after the polymerization reaction, X ¹ and X ^{2 at the} end of the polymer are groups that act as binding sites during the polymerization reaction. Therefore, the X ¹ and X ^2, in order to convert into a group that does not act as a binding site during the polymerization reaction, after the polymerization reaction, an alkyl group in X ¹ and X ^2, alkoxy group, alkyloxycarbonyl group, an aryl group And the like. In addition, it is conceivable to saturate the carbon-carbon double bonds of X ¹ and X ² by a catalytic hydrogenation reaction after the completion of the polymerization reaction, but the conversion method is not limited thereto.

When the compound represented by formula (VII) and the compound represented by formula (VI) are mixed, N ⁺ in the compound represented by formula (VI) is added to the cyclic part of the compound represented by formula (VII). A structure (A) in which an H ₂ group is included, that is, a rotaxane complex is formed. Here, the mixing ratio of the compound represented by the formula (VII) and the compound represented by the formula (VI) is 1 to 10: 1, preferably 1 to 3: 1, more preferably 1: 1 in molar ratio. is there. The formation of the rotaxane complex can be confirmed by ¹ H-NMR measurement.

The structure (A) is formed by mixing the compound represented by the formula (VII) and the compound represented by the formula (VI) in a solvent, and measuring the ¹ H-NMR of these compounds. The chemical shift of protons in the vicinity of the ammonium salt of the compound represented by can be confirmed by shifting to a low magnetic field.

(Second stage)
In the second stage of the production of the network polymer P of the present invention, the structure (A) formed in the first stage is polymerized (production of the network polymer P-1), or the structure (A) and the radical polymerizable monomer are polymerized. (Manufacture of network polymer P-2).
The pseudotaxane complex formed in the first step has a structure in which the polymerizable functional groups of X ^{1 to} X ⁴ are oriented in four directions, or a structure in which the polymerizable functional groups of X ³ and X ⁴ are oriented in two directions. . Then, X ¹ reactive polymerizable functional groups to X ^4, or a polymerization method by selecting, it is possible to control the structure of the network polymer after polymerization.

In the production of the network polymer P-1, the polymerization method is not limited as long as the structure (A) is polymerized, and the resulting network polymer includes the partial structures represented by the formulas (I) and (II), but the olefin metathesis is not limited. Reaction or radical polymerization reaction is preferred. The network polymer produced by the polymerization by olefin metathesis reaction has a structure in which a rotaxane unit is incorporated in the polymer main chain, while the network polymer by radical polymerization has a structure in which a rotaxane unit is incorporated in the polymer side chain.
Here, “the structure in which the rotaxane unit is incorporated in the polymer main chain” means a structure in which the rotaxane units are arranged along the extending direction of the polymer, and “the structure in which the rotaxane unit is incorporated in the polymer side chain”. Means that the rotaxane unit is located in a direction perpendicular to the direction of elongation of the polymer.

  In the production of the network polymer P-2, the polymerization reaction between the structure (A) and the radical polymerizable monomer is a partial structure represented by the formula (I) and the formula (II) in the network polymer produced by polymerization of these. As long as is included, the polymerization method is not limited, but a radical polymerization reaction is preferred. The radical polymerization reaction is not limited as long as the polymerizable functional group and the radical polymerizable monomer in the formula (V) and the formula (VI) react to generate a polymerization active site. For example, a method of exposing to heat or light, And a method of adding other active species, and a polymerization initiator, a reactive active species stabilizer, and the like may be added during the polymerization reaction. Here, the mixing ratio of the rotaxane complex and the radical polymerizable monomer is 1: 1 to 100, preferably 1: 2 to 50, more preferably 1: 5 to 10 in terms of molar ratio. Although reaction conditions are not specifically limited, Usually, it is made to react at room temperature-100 degreeC for 1 to 24 hours in organic solvents, such as chloroform and toluene.

The structure of the network polymer produced by the above method can be confirmed by ¹ H-NMR measurement, IR measurement or the like.

  The polymerization reaction is not limited as long as the polymerizable functional group in Formula (V) or Formula (VII) and Formula (VI) reacts to generate a polymerization active site. Examples thereof include a method of exposing to heat and light, a method of adding other active species, and the like, and a polymerization initiator, a stabilizer of reactive active species, and the like may be added during the polymerization reaction.

As the polymerization initiator to be used, those conventionally known may be used. For example, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylpropionamidine) disulfate, 2,2 '-Azobis (2-methylpropionamidine) dihydrochloride, 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis [2- (2-imidazoline-2
-Yl) propane] azo initiators such as dihydrochloride; persulfate initiators such as potassium persulfate and ammonium persulfate; peroxides such as benzoyl peroxide, t-butyl hydroperoxide and hydrogen peroxide An initiator etc. are mentioned.
In particular, as a photopolymerization initiator, acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, Triphenylamine, carbazole, 3-methylacetophenone, benzophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, 4,4′-diaminobenzophenone, benzoinpropyl ether, benzoin ethyl ether, benzyldimethyl ketal, 1- (4 -Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethyl Oxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) -butanone-1,4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6- Dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone) and the like can be mentioned. These polymerization initiators may be used alone or in combination of two or more.

[Manufacture of network polymer Q]
The network polymer P described above is further reacted with an electrophile, and the —N ⁺ H ₂ — group of the partial structure represented by the formula (II) is converted to —NR ^{5 of the} partial structure represented by the formula (II ′). -The network polymer Q can be produced by converting to a group (R ⁵ represents a residue derived from an electrophile).

As the electrophile, a —N ⁺ H ₂ — group having a partial structure represented by the formula (II) can be converted into a —NR ⁵ — group having a partial structure represented by the formula (II ′). There is no particular limitation as long as it is a linear or branched alkyl halide, linear or branched alkenyl halide, arylalkyl halide, acid halide, acid anhydride, carbonic acid halide, carbonic acid diester, alkylsulfonyl, for example. Halides, arylsulfonyl halides and the like can be mentioned. From the viewpoint of reducing steric hindrance to the cyclic portion, the electrophile preferably has about 1 to 11 carbon atoms.

  Specific examples of the linear or branched alkyl halide as the electrophile include methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, ethyl iodide, n-propyl chloride, N-propyl bromide, n-propyl iodide, i-propyl chloride, i-propyl bromide, i-propyl iodide, cyclopropyl chloride, cyclopropyl bromide, cyclopropyl iodide, n-butyl chloride, bromide n-butyl, n-butyl iodide, sec-butyl chloride, sec-butyl bromide, sec-butyl iodide, i-butyl chloride, i-butyl bromide, i-butyl iodide, tert-butyl chloride, odor Tert-butyl iodide, tert-butyl iodide, cyclobutyl chloride, cyclobutyl bromide, cyclobutyl iodide, pentyl chloride, pentyl bromide, pentyl iodide, Pentyl, neopentyl bromide, neopentyl iodide, amyl chloride, amyl bromide, amyl iodide, cyclopentyl chloride, cyclopentyl bromide, cyclopentyl iodide, hexyl chloride, hexyl bromide, hexyl iodide, cyclohexyl chloride, cyclohexyl bromide, Cyclohexyl iodide, heptyl chloride, heptyl bromide, heptyl iodide, octyl chloride, octyl bromide, octyl iodide, nonyl chloride, nonyl bromide, nonyl iodide, decyl chloride, decyl bromide, decyl iodide, undecyl chloride , Undecyl bromide, undecyl iodide, and the like.

  Specific examples of the linear or branched alkenyl group as the electrophile include vinyl chloride, vinyl bromide, vinyl iodide, allyl chloride, allyl bromide, allyl iodide, methacryl chloride, methacryl bromide. , Methacrylic iodide, crotonyl chloride, crotonyl bromide, crotonyl iodide, butenyl chloride, butenyl bromide, butenyl iodide, pentenyl chloride, pentenyl bromide, pentenyl iodide, cyclopentenyl chloride, cyclopentenyl bromide, cycloiodide iodide Pentenyl, hexenyl chloride, hexenyl bromide, hexenyl iodide, cyclohexenyl chloride, cyclohexenyl bromide, cyclohexenyl iodide, heptenyl chloride, heptenyl bromide, heptenyl iodide, octenyl chloride, octenyl bromide, octenyl iodide, chloride Nonenyl, nonenyl bromide, iodide Cycloalkenyl, decenyl chloride, bromide, decenyl, iodide decenyl, undecenyl chloride, bromide undecenyl, and the like iodide undecenyl is.

  Specific examples of the arylalkyl halide as the electrophile include benzyl chloride, benzyl bromide, benzyl iodide, cinnamilk chloride, cinnamyl bromide, cinnamyl iodide, hydrocinnamilk chloride, hydrocinnamyl bromide, hydro Cinnamyl iodide, naphthalene methyl chloride, naphthalene methyl bromide, naphthalene methyl iodide group and the like can be mentioned.

The —NR ⁺ H ₂ — group of the partial structure represented by the formula (II) using these linear or branched alkyl halides, linear or branched alkenyl halides, or arylalkyl halides _The method for converting to a ₅ -group is not particularly limited as long as it can be converted. For example, a -N ⁺ H ₂ -group having a partial structure represented by the formula (II) is converted to -NH using a base. Examples include a method in which a nitrogen anion is generated using a metal hydride after being converted to-, and reacted with a linear or branched alkyl halide, a linear or branched alkenyl halide, or an arylalkyl halide. At this time, the reactivity between the nitrogen anion and the nucleophile may be increased by adding a metal iodide or the like.

The base that can be 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 not particularly limited as long as it is a reaction solvent having no active hydrogen, and preferred solvents include tetrahydrofuran, N, N-dimethylformamide, hexamethylphosphoric triamide and the like.

  As the acid halide as the electrophile, formyl chloride, formyl bromide, acetyl chloride, acetyl bromide, propionyl chloride, propionyl bromide, acryloyl chloride, acryloyl bromide, propioroyl chloride, propioroyl bromide, butyryl chloride, butyryl bromide , Isobutyryl chloride, isobutyryl bromide, methacryloyl chloride, methacryloyl bromide, crotonoyl chloride, crotonoyl bromide, isocrotonoyl chloride, isocrotonoyl bromide, valeryl chloride, valeryl bromide, isovaleryl chloride, isovale Rilbromide, pivaloyl chloride, pivaloyl bromide, benzoic acid chloride, benzoic acid bromide, tolylic acid chloride, tolylic acid bromide, sodium Talenic acid chloride, naphthalene acid bromide, furancarboxylic acid chloride, furancarboxylic acid bromide, thiophenecarboxylic acid chloride, thiophenecarboxylic acid bromide, nicotinic acid chloride, nicotinic acid bromide, isonicotinic acid chloride, isonicotinic acid bromide, benzylcarbonyl chloride, Examples include benzylcarbonyl bromide, cinnamoyl chloride, cinnamoyl bromide, hydrocinnamoyl chloride, hydrocinnamoyl bromide, naphthalenyl acetyl chloride, naphthalenyl acetyl bromide and the like.

  Examples of the acid anhydride as the electrophile include formic anhydride, acetic anhydride, propionic anhydride, acrylic anhydride, propiolic anhydride, butanoic anhydride, isobutanoic anhydride, methacrylic anhydride, crotonic anhydride, isocrotonic anhydride , Barrelic anhydride, isovaleric anhydride, pivalic anhydride, benzoic anhydride, tolyric anhydride, naphthalene anhydride, furan carboxylic anhydride, thiophene carboxylic anhydride, nicotinic anhydride, isonicotinic anhydride, cinnam anhydride, hydrocinnam anhydride Examples include acid and naphthalenyl acetic anhydride.

  Carbonic acid halides as electrophiles include methoxycarbonyl chloride, ethoxycarbonyl chloride, n-propoxycarbonyl chloride, i-propoxycarbonyl chloride, n-butoxycarbonyl chloride, tert-butoxycarbonyl chloride, pentoxycarbonyl chloride, neopentyl. Examples thereof include oxycarbonyl chloride, amyloxycarbonyl chloride, hexyloxycarbonyl chloride, phenoxycarbonyl chloride, naphthyloxycarbonyl chloride, benzyloxycarbonyl chloride, tolyloxycarbonyl chloride, 9H-fluoren-9-ylmethoxycarbonyl chloride and the like.

  Anhydrous carbonic acid diester as the electrophile includes dimethyl carbonate, diethyl carbonate, di-n-propyl carbonate, di-i-propyl carbonate, di-n-butyl carbonate, di-tert-butyl carbonate, dipentyl carbonate, dineopentyl carbonate, diamyl carbonate , Dihexyl carbonate, diphenyl carbonate, ditolyl carbonate, dinaphthyl carbonate, dibenzyl carbonate, di (9H-fluoren-9-ylmethyl) carbonate, and the like.

  Examples of the alkylsulfonyl halide and arylsulfonyl halide as the electrophile include methanesulfonyl chloride, trifluoromethanesulfonyl chloride, camphorsulfonyl chloride, benzenesulfonyl chloride, toluenesulfonyl chloride, naphthalenesulfonyl chloride and the like.

Formula (II ′) of a —N ⁺ H ₂ — group having a partial structure represented by Formula (II) using acid halide, acid anhydride, carbonate halide, anhydride carbonic diester, alkylsulfonyl halide, arylsulfonyl halide, or the like ) -NR a partial structure represented by 5 ^- as the method of converting group, as long as the method can transform, is not particularly limited, for example, a base and the acid halide, acid anhydride, carbonate halides, carbonate anhydrous By allowing a diester, an alkylsulfonyl halide, an arylsulfonyl halide, or the like to coexist, a —N ⁺ H ₂ — group can be converted to a —NR ⁵ — group.

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.
The reaction solvent is not particularly limited as long as it is an aprotic solvent, and preferred solvents include acetonitrile, dichloromethane, N, N-dimethylformamide and the like.

The amount of the electrophile used is preferably 1.0 molar equivalent or more, more preferably 1.0 to 100.0 molar equivalent based on the formula (II). Although it is desirable conversion based, -NR 5 only part ^{- -} -N + ^H 2 in the repeating units derived from Formula (II) _- All groups -NR 5 also converted polymer network based on, Included in the present invention. The conversion rate of —N ⁺ H ₂ — group to —NR ⁵ — group may be 10% or more, preferably 30% or more, and more preferably 50% or more.

The network polymer P before reacting with the electrophile attracts the cyclic portion in the partial structure represented by the formula (I) and the —N ⁺ H ₂ — group in the partial structure represented by the formula (II). . Therefore, the movement of the crown ether ring in the axial direction in the solution or gel is limited to some extent. However, the mobility of the crown ether ring is improved by converting the —N ⁺ H ₂ — group to the —NR ⁵ — group by reaction with the electrophile.
The gelation ability with respect to the organic solvent is the same as that of the network polymer P. It can be confirmed by IR measurement that at least a part of the —N ⁺ H ₂ — group is converted to the —NR ⁵ — group.

The network polymer P and the network polymer Q have a gelling 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- Dioxane, acetonitrile, nitromethane, ethyl monoglyme, phosphate triester, trimethoxymethane, dioxolane derivative, sulfolane, 3-methyl-2-oxazolidinone, propylene carbonate derivative, tetrahydrofuran derivative, diethyl ether, 1,3-propane sultone And aprotic organic solvents such as These can also be used in mixture of 2 or more types.
In the present invention, gelation means that the fluidity of a fluid liquid is lost.

(2) Electrolyte solution containing magnesium salt The electrolyte solution containing magnesium salt is not particularly limited as long as it can be used for the polymer gel electrolyte of the present invention. Examples of the magnesium salt include Mg (OH ) ₂ , MgCl ₂ , Mg (NO ₃ ) ₂ , Mg (BF ₄ ) ₂ , Mg (PF ₆ ) ₂ , Mg (ClO ₄ ) ₂ , Mg (CF ₃ SO ₃ ) ₂ , Mg (AsF ₆ ) ₂ , Mg (ClO ₄ ) ₂ , MgCl ₂ , Mg (CF ₃ SO ₃ ) ₂ , Mg (TFSA) ₂ [Mg (N (CF ₃ SO ₂ ) ₂ ) ₂ ] can be mentioned. In particular, Mg (TFSA) ₂ is preferable. You may use the said magnesium salt 1 type or in mixture of 2 or more types.

  The solvent used for the preparation of the electrolyte solution containing the magnesium salt is not particularly limited as long as it can be used for the polymer gel electrolyte of the present invention and can dissolve the above magnesium salt. , 2-dimethoxyethane, acetonitrile, propylene carbonate, ethylene carbonate, 3-methoxypropionitrile, methoxyacetonitrile, ethylene glycol, propylene glycol, deethylene glycol, triethylene glycol, butyl rholactone, demethoxyethane, demethyl carbonate, 1,3-deoxolane, methyl poromate, 2-methyltetrahydrofuran, 3-methoxy-oxazolidene-2-one, sulfolane, tetrahydrofuran, triethylene glycol dimethyl ether ( riglyme), water, etc. can be included. In particular, triethylene glycol dimethyl ether (Triglyme) is preferable. The said solvent can be used 1 type or in mixture of 2 or more types. The concentration of the magnesium salt in the electrolyte solution is preferably about 0.2 to 3.0 mol / L, for example.

  The polymer gel electrolyte of the present invention is obtained by mixing an electrolyte solution containing (1) a rotaxane network polymer and (2) a magnesium salt. Since the rotaxane network polymer has a gelling ability with respect to various solvents, a polymer gel electrolyte is formed by mixing an electrolyte solution containing a rotaxane network polymer and a magnesium salt.

Specifically, a production method in which a predetermined amount of rotaxane network polymer is dissolved by heating in an electrolyte solution containing a predetermined amount of magnesium salt and cooled is exemplified. Usually, it is preferable to dissolve completely by heating.
When the rotaxane network polymer is used, the content of the electrolyte solution containing the magnesium salt can be reduced. However, the polymer gel electrolyte using the network polymer Q is compared with the polymer gel electrolyte using the network polymer P. The content of the electrolyte solution can be further reduced.
That is, the usage-amount of the electrolyte solution containing the magnesium salt with respect to the network polymer P is 10-300 mass parts with respect to 100 mass parts of network polymers P, Preferably it is 100-200 mass parts.
On the other hand, the usage-amount of the electrolyte solution containing the magnesium salt with respect to the network polymer Q is 10-100 mass parts with respect to 100 mass parts of network polymers Q, Preferably it is 10-50 mass parts.

(Magnesium secondary battery)
The polymer gel electrolyte of the present invention can be used for a magnesium secondary battery. The magnesium secondary battery of the present invention can apply various components and structures employed in conventionally known non-aqueous electrolyte secondary batteries except that the polymer gel electrolyte is used.

The positive electrode of the magnesium secondary battery of the present invention is not particularly limited as long as it absorbs positive ions during discharge or discharges negative ions, and is a metal such as MgFeSiO ₄ or vanadium pentoxide (V ₂ O ₅ ). Conventionally known materials can be used as positive electrode materials for secondary batteries such as oxides, polyacetylene, polyaniline, polypyrrole, polythiophene, polyparaphene, and other conductive polymers and their derivatives, and disulfide compounds. Moreover, the organic sulfur material reported by the present applicants can also be used as a positive electrode.
Among these positive electrodes, vanadium pentoxide (V ₂ O ₅ ) and organic sulfur materials are preferable.

As the organic sulfur material, the following sulfur-containing network polymer obtained by reacting diallyl compound (VIII) or allyl compound (IX) with solid sulfur (S ₈ ) described in Japanese Patent Application No. 2014-095144 Polymers can be used.

Formula (VIII)

[In Formula (VIII), R ¹ ′ and R ³ ′ each independently represent a linking group represented by —COO—, —OCO—, —CONH—, —NHCO—, or —O—, a substituted or Any one selected from the group consisting of an unsubstituted straight chain or branched alkylene group having 1 to 20 carbon atoms, and —COO—, —OCO—, —CONH—, —NHCO—, and —O— as a linking group. Any one selected from the group consisting of a substituted or unsubstituted linear or branched alkylene group having 1 to 19 carbon atoms having one or two, and R ² ′ is substituted or unsubstituted. A linear or branched alkylene group having 2 to 20 carbon atoms, a substituted or unsubstituted linear or branched alkylene group having 1 or more —O— in the main chain, substituted or non-substituted Substituted aromatic group, substituted or unsubstituted C3-C7 cycloal The alkylene group and the following formula
(In the formula, n ⁵ and n ⁶ are each independently an integer of 1 to 4,
A bond represented by a broken line represents bonding to the 3-position or 4-position of the benzene ring), or a diallyl compound represented by formula (IX)
(Wherein R ⁴ ′ represents a substituted or unsubstituted linear or branched alkyl group having 5 to 20 carbon atoms) and molecular sulfur (S ₈ ) are mixed. A sulfur-containing polymer obtained by heating.

The sulfur-containing polymer is a network polymer obtained by mixing and heating a diallyl compound or monoallyl compound and molecular sulfur (S ₈ ), and the diallyl compound or monoallyl compound is represented by the following formula (VIII): Alternatively, the compound is not particularly limited as long as it is a compound represented by (IX) (hereinafter referred to as compound (VIII) or (IX); the same applies to compounds of other formula numbers).

  The “straight chain or branched alkylene group having 1 to 20 carbon atoms” of the “substituted or unsubstituted linear or branched alkylene group having 1 to 20 carbon atoms” means a divalent saturated carbon number of 1 -20 carbon chain, specifically methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, heptadecylene, octadecylene, nonadecylene And icosylene.

  The ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, heptadecylene, octadecylene, nonadecylene, and icosylene include all structural isomers thereof.

  As the substituent of the above-mentioned “substituted or unsubstituted linear or branched alkylene group having 1 to 20 carbon atoms”, a hydroxyl group, a fluorine atom, an aromatic group, a dialkylamino group, an alkyloxycarbonyl group shown below, An alkoxy group, a nitrogen-containing heterocyclic group, etc. can be mentioned.

  The alkyl in the dialkylamino group, alkyloxycarbonyl group, and alkoxy group is a linear or branched alkyl having 1 to 4 carbon atoms, specifically, methyl, ethyl, n-propyl, isopropyl, n -Butyl, s-butyl, t-butyl, isobutyl.

  Specific examples of the nitrogen-containing heterocyclic group include pyrrolidine, pyrazolidine, imidazolidine, oxazolidine, isoxazolidine, piperidine, piperazine, morpholine, thiomorpholine, and the like.

The above-mentioned “a substituted or unsubstituted linear or branched group having any one or two selected from the group consisting of —COO—, —OCO—, —CONH—, —NHCO—, and —O— as a linking group; Any one or two selected from the group consisting of —COO—, —OCO—, —CONH—, —NHCO—, and —O— as the linking group in the branched alkylene group having 1 to 19 carbon atoms. The term “straight chain or branched alkylene group having 1 to 19 carbon atoms” means that the straight chain or branched alkylene group having 1 to 19 carbon atoms is allyl via an ester bond, an amide bond and / or an ether bond. Group and R ² ′, specifically, in the relationship with allyl group and R ² ′, allyl group-alkylene group-COO-R ² ′, allyl group-alkylene group-OCO-R ² ′. Allyl group-alkylene group- ^{ONH-R 2} ', an allyl group - alkylene group ^{-NHCO-R 2',} an allyl group - alkylene group ^{-O-R 2} ', an allyl group -COO- alkylene group -R ^2', an allyl group -COO- alkylene group - ^{COO-R 2} ', an allyl group -COO- alkylene group ^{-OCO-R 2',} an allyl group -COO- alkylene group ^{-CONH-R 2} ', an allyl group -COO- alkylene group ^{-NHCO-R 2',} an allyl group -COO- alkylene group ^{-O-R 2} ', an allyl group -OCO- alkylene group -R ^2', an allyl group -OCO- alkylene group ^{-COO-R 2} ', an allyl group -OCO- alkylene group ^{--OCO-R 2} ', an allyl group -OCO- alkylene group ^{-CONH-R 2',} an allyl group -OCO- alkylene group ^{-NHCO-R 2} ', an allyl group -OCO- alkylene group ^{-O-R 2',} an allyl group - ONH- alkylene group -R ² ', an allyl group -CONH- alkylene group ^{-COO-R 2',} an allyl group -CONH- alkylene group ^{-OCO-R 2} ', an allyl group -CONH- alkylene group ^{-CONH-R 2'} , allyl group -CONH- alkylene group ^{-NHCO-R 2} ', an allyl group -OCO- alkylene group ^{-O-R 2',} an allyl group -NHCO- alkylene group -R ² ', an allyl group -NHCO- alkylene group -COO -R ² ', an allyl group -NHCO- alkylene group ^{-OCO-R 2',} an allyl group -NHCO- alkylene group ^{-CONH-R 2} ', an allyl group -NHCO- alkylene group ^{-NHCO-R 2',} an allyl group - NHCO- alkylene group ^{-O-R 2} ', an allyl group -O- alkylene group -R ^2', an allyl group -O- alkylene group ^{-COO-R 2} ', an allyl group -O- A Alkylene group ^{-CONH-R 2 ', -NHCO-} R 2 an allyl group -O- alkylene group', ^{--OCO-R 2} an allyl group -O- alkylene group ', and allyl group -O- alkylene group ^{-O-R 2} Represented by '.
At this time, it is preferable that the carbon atom of the alkylene group to which the oxygen atom is bonded does not have a substituent substituted with a heteroatom such as a dialkylamino group, an alkoxy group, or a nitrogen-containing heterocyclic group.

  The above-mentioned “a substituted or unsubstituted linear or branched group having any one or two selected from the group consisting of —COO—, —OCO—, —CONH—, —NHCO—, and —O— as a linking group; Examples of the substituent of the “branched alkylene group having 1 to 19 carbon atoms” include the same substituents as those of the above-mentioned “substituted or unsubstituted linear or branched alkylene group having 1 to 20 carbon atoms”. .

R ¹ ′ and R ³ ′ may be any of the aforementioned groups, but preferably hexylene, heptylene, octylene, —COO-hexylene, —COO-heptylene, —COO-octylene, — O-hexylene, -O-heptylene, -O-octylene, -OCO-hexylene, -OCO-heptylene, and -OCO-octylene, more preferably -COO-hexylene, -COO-heptylene, -COO -Octylene, -OCO-hexylene, -OCO-heptylene, and -OCO-octylene, more preferably -OCO-hexylene, -OCO-heptylene, and -OCO-octylene, most preferably an allyl group and 'in relation to the allyl - hexylene ^{-COO-R 2' R 2,} an allyl group - hept Emissions ^{-COO-R 2} ', and allyl groups - octylene ^{-COO-R 2'} is.

The above-mentioned “substituted or unsubstituted linear or branched alkylene group having 2 to 20 carbon atoms” is the substituted or unsubstituted linear or branched carbon number of 1 shown for R ¹ ′ and R ³ ′. The same thing as the alkylene group of -20 can be mentioned.

  The substituent of the “substituted or unsubstituted linear or branched alkylene group having 2 to 20 carbon atoms” is the above-mentioned “substituted or unsubstituted linear or branched alkylene group having 1 to 20 carbon atoms”. This is the same as the substituent.

As the above-mentioned “substituted or unsubstituted linear or branched alkylene group having 2 to 20 carbon atoms having at least one —O— in the main chain”
-(O-linear or branched alkylene having 2 to 20 carbon atoms) _m1- ,
-(O-straight chain or branched alkylene having 2 to 20 carbon atoms) _m1 -O-, and -straight chain or branched alkylene having 2 to 20 carbon atoms- (O-straight chain or branched carbon number) 2-20 alkylene) _m2 −
(Poly) ether group represented as
The m1 is an integer of 1 to 10, the m2 is an integer of 1 to 9, and m1 and m2 are substituted or unsubstituted linear or branched having one or more of —O—. The total carbon number of the main chain of the alkylene group having 2 to 20 carbon atoms is determined to be 2 to 20.

-(O-linear or branched alkylene having 2 to 20 carbon atoms) _m1 -,-(O-linear or branched alkylene having 2 to 20 carbon atoms) _m1- O-, and _-linear Or a branched alkylene group having 2 to 20 carbon atoms (O-straight chain or branched alkylene group having 2 to 20 carbon atoms) _m2 − in relation to R ¹ and R ³ ,
R ¹ '- (O- straight chain or branched alkylene of 2 to 20 carbon _atoms) m1 -R ^3',
R ¹ ′-(Linear or branched alkylene having 2 to 20 carbon atoms) _m1- R ³ ′,
R ¹ ′-(O—straight chain or branched alkylene having 2 to 20 carbon atoms) _m1— O—R ³ ′,
R ¹ ′ -straight chain or branched alkylene having 2 to 20 carbon atoms— (O—straight chain or branched alkylene having 2 to 20 carbon atoms) _m2- R ³ ′,
R ^1, etc. '- - _{m @ 2} (alkylene -O linear or branched _C2-20) alkylene -R ³ having 2 to 20 carbon atoms of straight-chain or branched' and the like.

“Linear or branched having one or more —O— in the main chain” of the above-mentioned “substituted or unsubstituted linear or branched alkylene group having 2 to 20 carbon atoms having one or more —O— in the main chain” Specific examples of the branched alkylene group having 2 to 20 carbon atoms include -O-ethylene-, -O-ethylene-O-, -O-ethylene-O-ethylene-, and -O-ethylene-O-ethylene. -O-, -ethylene-O-ethylene-, -O-ethylene-O-propylene-, -O-ethylene-O-propylene-O-, -ethylene-O-propylene-, -O-ethylene-O-butylene -, -O-ethylene-O-butylene-O-, -ethylene-O-butylene-, -O-ethylene-O-pentylene-, -O-ethylene-O-pentylene-O-, -ethylene-O-pentylene. -, -O-ethylene-O-hexylene-, -O- Tylene-O-hexylene-O-, -ethylene-O-hexylene-, -O-ethylene-O-heptylene-, -O-ethylene-O-heptylene-O-, -ethylene-O-heptylene-,- O-ethylene-O-octylene-, -O-ethylene-O-octylene-O-, -ethylene-O-octylene-, -O-ethylene-O-nonylene-, -O-ethylene-O-nonylene-O- , -Ethylene-O-nonylene-, -O-ethylene-O-decylene-, -O-ethylene-O-decylene-O-, -ethylene-O-decylene-, -O-ethylene-O-ethylene-O- Ethylene-, -O-ethylene-O-ethylene-O-ethylene-O-, -ethylene-O-ethylene-O-ethylene-, -O-ethylene-O-propylene-O-ethylene-, -O-ethylene- O-P Pyrene-O-ethylene-O-, -ethylene-O-propylene-O-ethylene-, -O-ethylene-O-propylene-O-propylene-, -O-ethylene-O-propylene-O-propylene-O- , -Ethylene-O-propylene-O-propylene-, -ethylene-O-propylene-O-butylene-, -O-ethylene-O-propylene-O-butylene-, -O-ethylene-O-propylene-O- Butylene-O-, -O-ethylene-O-propylene-O-pentylene-, -O-ethylene-O-propylene-O-pentylene-O-, -ethylene-O-propylene-O-pentylene-, -O- Ethylene-O-propylene-O-hexylene, -O-ethylene-O-propylene-O-hexylene-O-, -ethylene-O-propylene-O-hexylene, -O-ethylene-O-propylene-O-heptylene-, -O-ethylene-O-propylene-O-heptylene-O-, -ethylene-O-propylene-O-heptylene-, -O-ethylene-O-butylene -O-ethylene-, -O-ethylene-O-butylene-O-ethylene-O-, -ethylene-O-butylene-O-ethylene-, -O-ethylene-O-pentylene-O-ethylene-, -O -Ethylene-O-pentylene-O-ethylene-O-, -ethylene-O-pentylene-O-ethylene-, -O-ethylene-O-butylene-O-propylene-, -O-ethylene-O-butylene-O -Propylene-O-, -Ethylene-O-butylene-O-propylene-, -O-ethylene-O-butylene-O-butylene-, -O-ethylene-O-butylene-O-butylene- -, -Ethylene-O-butylene-O-butylene-, -O-ethylene-O-butylene-O-pentylene-, -O-ethylene-O-butylene-O-pentylene-O-, -ethylene-O-butylene -O-pentylene-, -O-ethylene-O-butylene-O-hexylene-, -O-ethylene-O-butylene-O-hexylene-O-, -ethylene-O-butylene-O-hexylene-, -O -Ethylene-O-pentylene-O-ethylene-, -O-ethylene-O-pentylene-O-ethylene-O-, -ethylene-O-pentylene-O-ethylene-, -O-ethylene-O-pentylene-O -Propylene-, -O-ethylene-O-pentylene-O-propylene-O-, -ethylene-O-pentylene-O-propylene-, -O-ethylene-O-pentylene-O- Tylene-, -O-ethylene-O-pentylene-O-butylene-O-, -ethylene-O-pentylene-O-butylene-, -O-ethylene-O-pentylene-O-pentylene-, -O-ethylene- O-pentylene-O-pentylene-O-, -ethylene-O-pentylene-O-pentylene-, -O-ethylene-O-hexylene-O-ethylene-, -O-ethylene-O-hexylene-O-ethylene- O-, -ethylene-O-hexylene-O-ethylene-, -O-ethylene-O-hexylene-O-propylene-, -O-ethylene-O-hexylene-O-propylene-O-, -ethylene-O- Hexylene-O-propylene-, -O-ethylene-O-hexylene-O-butylene-, -O-ethylene-O-hexylene-O-butylene-O-, -ethylene-O- Hexylene-O-butylene-, -O-ethylene-O-heptylene-O-ethylene-, -O-ethylene-O-heptylene-O-ethylene-O-, -ethylene-O-heptylene-O-ethylene-,- O-ethylene-O-heptylene-O-propylene-, -O-ethylene-O-heptylene-O-propylene-O-, -ethylene-O-heptylene-O-propylene-, -O-ethylene-O-octylene- O-ethylene-, -O-ethylene-O-octylene-O-ethylene-O-, -ethylene-O-octylene-O-ethylene-, -O-ethylene-O-ethylene-O-ethylene-O-ethylene- , -O-ethylene-O-ethylene-O-ethylene-O-ethylene-O-, -ethylene-O-ethylene-O-ethylene-O-ethylene-, -O-ethylene-O- Tylene-O-ethylene-O-propylene-, -O-ethylene-O-ethylene-O-ethylene-O-propylene-O-, -ethylene-O-ethylene-O-ethylene-O-propylene-, -O- Ethylene-O-ethylene-O-ethylene-O-butylene-, -O-ethylene-O-ethylene-O-ethylene-O-butylene-O-, -ethylene-O-ethylene-O-ethylene-O-butylene- -O-ethylene-O-ethylene-O-ethylene-O-pentylene-, -O-ethylene-O-ethylene-O-ethylene-O-pentylene-O-, -ethylene-O-ethylene-O-ethylene- O-pentylene, -O-ethylene-O-ethylene-O-ethylene-O-hexylene-O-, -O-ethylene-O-ethylene-O-ethylene-O-hexylene, -eth -O-ethylene-O-ethylene-O-hexylene-, -O-ethylene-O-ethylene-O-propylene-O-ethylene-, -O-ethylene-O-ethylene-O-propylene-O-ethylene- O-, -ethylene-O-ethylene-O-propylene-O-ethylene-, -O-ethylene-O-ethylene-O-propylene-O-propylene-, -O-ethylene-O-ethylene-O-propylene- O-propylene-O-, -ethylene-O-ethylene-O-propylene-O-propylene-, -O-ethylene-O-ethylene-O-propylene-O-butylene-, -O-ethylene-O-ethylene- O-propylene-O-butylene-O-, -ethylene-O-ethylene-O-propylene-O-butylene-, -O-ethylene-O-ethylene-O-propylene-O-pe N-ylene, -O-ethylene-O-ethylene-O-propylene-O-pentylene-O-, -ethylene-O-ethylene-O-propylene-O-pentylene-, -O-ethylene-O-ethylene-O- Butylene-O-ethylene-, -O-ethylene-O-ethylene-O-butylene-O-ethylene-O-, -ethylene-O-ethylene-O-butylene-O-ethylene-, -O-ethylene-O- Ethylene-O-butylene-O-propylene-, -O-ethylene-O-ethylene-O-butylene-O-propylene-O-, -ethylene-O-ethylene-O-butylene-O-propylene-, -O- Ethylene-O-ethylene-O-butylene-O-butylene-, -O-ethylene-O-ethylene-O-butylene-O-butylene-O-, -ethylene-O-ethylene-O-butylene -O-butylene-, -O-ethylene-O-ethylene-O-pentylene-O-ethylene-, -O-ethylene-O-ethylene-O-pentylene-O-ethylene-O-, -ethylene-O-ethylene -O-pentylene-O-ethylene-, -O-ethylene-O-ethylene-O-pentylene-O-propylene-, -O-ethylene-O-ethylene-O-pentylene-O-propylene-O-, -ethylene -O-ethylene-O-pentylene-O-propylene-, -O-ethylene-O-ethylene-O-hexylene-O-ethylene-, -O-ethylene-O-ethylene-O-hexylene-O-ethylene-O -, -Ethylene-O-ethylene-O-hexylene-O-ethylene-, -O-ethylene-O-propylene-O-ethylene-O-propylene-, -O-ethylene-O Propylene-O-ethylene-O-propylene-O-, -ethylene-O-propylene-O-ethylene-O-propylene-, -O-ethylene-O-propylene-O-ethylene-O-butylene-, -O- Ethylene-O-propylene-O-ethylene-O-butylene-O-, -ethylene-O-propylene-O-ethylene-O-butylene-, -O-ethylene-O-propylene-O-ethylene-O-pentylene- -O-ethylene-O-propylene-O-ethylene-O-pentylene-O-, -ethylene-O-propylene-O-ethylene-O-pentylene-, -O-ethylene-O-propylene-O-propylene- O-ethylene-, -O-ethylene-O-propylene-O-propylene-O-ethylene-O-, -ethylene-O-propylene-O-propylene-O- Ethylene-, -O-ethylene-O-propylene-O-butylene-O-ethylene-, -O-ethylene-O-propylene-O-butylene-O-ethylene-O-, -ethylene-O-propylene-O- Butylene-O-ethylene-, -O-ethylene-O-propylene-O-pentylene-O-ethylene-, -O-ethylene-O-propylene-O-pentylene-O-ethylene-O-, -ethylene-O- Propylene-O-pentylene-O-ethylene-, -O-ethylene-O-butylene-O-ethylene-O-propylene-, -O-ethylene-O-butylene-O-ethylene-O-propylene-O-,- Ethylene-O-butylene-O-ethylene-O-propylene-, -O-ethylene-O-butylene-O-ethylene-O-butylene-, -O-ethylene-O-butylene- -Ethylene-O-butylene-O-, -Ethylene-O-butylene-O-ethylene-O-butylene-, -O-ethylene-O-ethylene-O-ethylene-O-ethylene-O-ethylene-, -O -Ethylene-O-ethylene-O-ethylene-O-ethylene-O-ethylene-O-, -ethylene-O-ethylene-O-ethylene-O-ethylene-O-ethylene-, -O-ethylene-O-ethylene -O-ethylene-O-ethylene-O-propylene-, -O-ethylene-O-ethylene-O-ethylene-O-ethylene-O-butylene-, -O-ethylene-O-ethylene-O-ethylene-O -Ethylene-O-propylene-O-, -O-ethylene-O-ethylene-O-ethylene-O-ethylene-O-butylene-O-, -ethylene-O-ethylene-O-ethylene-O- -O-ethylene-O-ethylene-O-ethylene-O-ethylene-O-butylene-, -O-ethylene-O-ethylene-O-ethylene-O-propylene-O-ethylene-,- O-ethylene-O-ethylene-O-ethylene-O-butylene-O-ethylene-, -O-ethylene-O-ethylene-O-ethylene-O-propylene-O-ethylene-O-, -O-ethylene- O-ethylene-O-ethylene-O-butylene-O-ethylene-O-, -ethylene-O-ethylene-O-ethylene-O-propylene-O-ethylene-, -ethylene-O-ethylene-O-ethylene- O-butylene-O-ethylene-, -O-ethylene-O-ethylene-O-propylene-O-ethylene-O-ethylene-, -O-ethylene-O-ethylene-O-butylene-O -Ethylene-O-ethylene-, -O-ethylene-O-ethylene-O-propylene-O-ethylene-O-ethylene-O-, -O-ethylene-O-ethylene-O-butylene-O-ethylene-O -Ethylene-O-,
-Ethylene-O-ethylene-O-propylene-O-ethylene-O-ethylene-, -ethylene-O-ethylene-O-butylene-O-ethylene-O-ethylene-, -O-ethylene-O-ethylene-O -Ethylene-O-ethylene-O-ethylene-O-ethylene-, -O-ethylene-O-ethylene-O-ethylene-O-ethylene-O-ethylene-O-ethylene-O-, -ethylene-O-ethylene -O-ethylene-O-ethylene-O-ethylene-O-ethylene-, -O-ethylene-O-ethylene-O-ethylene-O-ethylene-O-ethylene-O-ethylene-O-ethylene-, -O -Ethylene-O-ethylene-O-ethylene-O-ethylene-O-ethylene-O-ethylene-O-ethylene-O-, -ethylene-O-ethylene-O-ethylene-O-ethylene O-ethylene-O-ethylene-O-ethylene-, -O-ethylene-O-ethylene-O-ethylene-O-ethylene-O-ethylene-O-ethylene-O-ethylene-O-ethylene-, -O- Ethylene-O-ethylene-O-ethylene-O-ethylene-O-ethylene-O-ethylene-O-ethylene-O-ethylene-O-, -ethylene-O-ethylene-O-ethylene-O-ethylene-O- Ethylene-O-ethylene-O-ethylene-O-ethylene-, -O-ethylene-O-ethylene-O-ethylene-O-ethylene-O-ethylene-O-ethylene-O-ethylene-O-ethylene-O- Ethylene-, -O-ethylene-O-ethylene-O-ethylene-O-ethylene-O-ethylene-O-ethylene-O-ethylene-O-ethylene-O-ethylene-O-, ethylene -O-ethylene-O-ethylene-O-ethylene-O-ethylene-O-ethylene-O-ethylene-O-ethylene-O-ethylene-, -O-ethylene-O-ethylene-O-ethylene-O-ethylene -O-ethylene-O-ethylene-O-ethylene-O-ethylene-O-ethylene-O-ethylene-, -O-ethylene-O-ethylene-O-ethylene-O-ethylene-O-ethylene-O-ethylene -O-ethylene-O-ethylene-O-ethylene-O-ethylene-O-, -ethylene-O-ethylene-O-ethylene-O-ethylene-O-ethylene-O-ethylene-O-ethylene-O-ethylene -O-ethylene-O-ethylene-, -O-propylene-, -O-propylene-O-, -O-propylene-O-propylene-, -O-propylene-O-propylene-O-. -Propylene-O-propylene-, -O-propylene-O-butylene-, -O-propylene-O-butylene-O-, -propylene-O-butylene-, -O-propylene-O-pentylene-,- O-propylene-O-pentylene-O-, -propylene-O-pentylene-, -O-propylene-O-hexylene-, -O-propylene-O-hexylene-O-, -propylene-O-hexylene -, -O-propylene-O-heptylene-, -O-propylene-O-heptylene-O-, -propylene-O-heptylene-, -O-propylene-O-octylene-, -O-propylene-O-octylene. -O-, -propylene-O-octylene-, -O-propylene-O-nonylene-, -O-propylene-O-nonylene-O-, -propylene-O-nonylene. -O-propylene-O-ethylene-O-propylene-, -O-propylene-O-ethylene-O-propylene-O-, -propylene-O-ethylene-O-propylene-, -O-propylene-O- Ethylene-O-butylene-, -O-propylene-O-ethylene-O-butylene-O-, -propylene-O-ethylene-O-butylene-, -O-propylene-O-ethylene-O-pentylene-,- O-propylene-O-ethylene-O-pentylene-O-, -propylene-O-ethylene-O-pentylene-, -O-propylene-O-ethylene-O-hexylene-, -O-propylene-O-ethylene- O-hexylene-O-, -propylene-O-ethylene-O-hexylene-, -O-propylene-O-ethylene-O-heptylene-, -O-propylene- -Ethylene-O-heptylene-O-, -propylene-O-ethylene-O-heptylene-, -O-propylene-O-propylene-O-propylene-, -O-propylene-O-propylene-O-propylene-O -, -Propylene-O-propylene-O-propylene, -O-propylene-O-propylene-O-butylene-, -O-propylene-O-propylene-O-butylene-O-, -propylene-O-propylene -O-butylene-, -O-propylene-O-propylene-O-pentylene-, -O-propylene-O-propylene-O-pentylene-O-, -propylene-O-propylene-O-pentylene-, -O -Propylene-O-propylene-O-hexylene-, -O-propylene-O-propylene-O-hexylene-O-, -propylene-O -Propylene-O-hexylene-, -O-propylene-O-butylene-O-propylene-, -O-propylene-O-butylene-O-propylene-O-, -propylene-O-butylene-O-propylene-, -O-propylene-O-butylene-O-butylene-, -O-propylene-O-butylene-O-butylene-O-, -propylene-O-butylene-O-butylene-, -O-propylene-O-butylene -O-pentylene-, -O-propylene-O-butylene-O-pentylene-O-, -propylene-O-butylene-O-pentylene-, -O-propylene-O-pentylene-O-propylene-, -O -Propylene-O-pentylene-O-propylene-O-, -propylene-O-pentylene-O-propylene-, -O-propylene-O-pentylene- -Butylene-, -O-propylene-O-pentylene-O-butylene-O-, -propylene-O-pentylene-O-butylene-, -O-propylene-O-hexylene-O-propylene-, -O-propylene -O-hexylene-O-propylene-O-, -propylene-O-hexylene-O-propylene, -O-propylene-O-propylene-O-propylene-O-propylene-, -O-propylene-O-propylene -O-propylene-O-propylene-O-, -propylene-O-propylene-O-propylene-O-propylene-, -O-propylene-O-propylene-O-propylene-O-propylene-O-propylene-, -O-propylene-O-propylene-O-propylene-O-propylene-O-propylene-O-, -propylene-O- Lopylene-O-propylene-O-propylene-O-propylene-, -O-propylene-O-propylene-O-propylene-O-propylene-O-propylene-O-propylene-, -O-propylene-O-propylene- O-propylene-O-propylene-O-propylene-O-propylene-O-, -propylene-O-propylene-O-propylene-O-propylene-O-propylene-O-propylene-, -O-butylene-,- O-butylene-O-, -O-butylene-O-butylene-, -O-butylene-O-pentylene-, -O-butylene-O-hexylene-, -O-butylene-O-heptylene-, -O- Butylene-O-octylene-, -O-butylene-O-butylene-O-, -O-butylene-O-pentylene-O-, -O-butylene-O-hex Silene-O-, -O-butylene-O-heptylene-O-, -O-butylene-O-octylene-O-, -butylene-O-butylene-, -butylene-O-pentylene-, -butylene-O- Hexylene-, -butylene-O-heptylene-, -butylene-O-octylene-, -O-butylene-O-ethylene-O-butylene-, -O-butylene-O-ethylene-O-butylene-O-,- Butylene-O-ethylene-O-butylene-, -O-butylene-O-propylene-O-butylene-, -O-butylene-O-propylene-O-butylene-O-, -butylene-O-propylene-O- Butylene-, -O-butylene-O-butylene-O-butylene-, -O-butylene-O-butylene-O-butylene-O-, -butylene-O-butylene-O-butylene-, -O-butyl Len-O-butylene-O-butylene-O-butylene-, -O-butylene-O-butylene-O-butylene-O-butylene-O-, -butylene-O-butylene-O-butylene-O-butylene- -O-butylene-O-butylene-O-butylene-O-butylene-O-butylene-, -O-butylene-O-butylene-O-butylene-O-butylene-O-butylene-O-, -butylene- O-butylene-O-butylene-O-butylene-O-butylene-, -O-pentylene-, -O-pentylene-O-, -O-pentylene-O-pentylene-, -O-pentylene-O-pentylene- O-, -pentylene-O-pentylene-, -O-pentylene-O-hexylene-, -O-pentylene-O-hexylene-O-, -pentylene-O-hexylene-, -O-pentylene -O-heptylene-, -O-pentylene-O-heptylene-O-, -pentylene-O-hexylene-, -pentylene-O-heptylene-, -O-pentylene-O-ethylene-O-pentylene-, -O-pentylene-O-ethylene-O-pentylene-O-, -pentylene-O-ethylene-O-pentylene-, -O-pentylene-O-pentylene-O-pentylene-, -O-pentylene-O-pentylene. -O-pentylene-O-, -pentylene-O-pentylene-O-pentylene-, -O-pentylene-O-pentylene-O-pentylene-O-pentylene-, -O-pentylene-O-pentylene-O-pentylene -O-pentylene-O-, -pentylene-O-pentylene-O-pentylene-O-pentylene-, -O-hexylene-, -O-hex Silene-O-, -O-hexylene-O-hexylene-, -O-hexylene-O-hexylene-O-, -hexylene-O-hexylene-, -O-hexylene-O- Xylene-O-hexylene-, -O-hexylene-O-hexylene-O-hexylene-O-, -hexylene-O-hexylene-O-hexylene-, -O-heptylene-, -O -Heptylene-O-, -O-heptylene-O-heptylene-, -O-heptylene-O-heptylene-O-, -heptylene-O-heptylene-, -O-octylene-, -O-octylene-O-, -O-octylene-O-octylene-, -O-octylene-O-octylene-O-, -octylene-O-octylene-, -O-nonylene-, -O-nonylene-O-, -O-nonylene-O -Nonylene-, -O-Nonile -O-nonylene-O-, -nonylene-O-nonylene-, -O-decylene-, -O-decylene-O-, -O-decylene-O-decylene-, -O-decylene-O-decylene-O -, -Decylene-O-decylene-, -O-undecylene-, -O-undecylene-O-, -O-dodecylene-, -O-dodecylene-O-, -O-tridecylene-, -O-tridecylene-O -, -O-tetradecylene-, -O-tetradecylene-O-, -O-pentadecylene-, -O-pentadecylene-O-, -O-hexadecylene-, -O-hexadecylene-O-, -O-heptadecylene-, -O-heptadecylene-O-, -O-octadecylene-, -O-octadecylene-O-, -O-nonadecylene-, -O-nonadecylene-O-, -O-icosylene-, -O-ico It can be mentioned Ren -O- and the like.

  Examples of the substituent of the above-mentioned “substituted or unsubstituted linear or branched alkylene group having 2 to 20 carbon atoms having one or more —O— in the main chain” include the above “substituted or unsubstituted linear or branched. This is the same as the substituent of the “branched alkylene group having 1 to 20 carbon atoms”.

  The substituent of the above-mentioned “substituted or unsubstituted linear or branched alkylene group having 2 to 20 carbon atoms having one or more —O—” is a hydroxyl group, a dialkylamino group, an alkoxy group, a nitrogen-containing heterocyclic group, or the like. In some cases, it is preferable that the substituent is not present on the carbon atom bonded to the oxygen atom.

  The “aromatic group” of the “substituted or unsubstituted aromatic group” is a divalent aromatic ring, and specifically, as the aromatic ring, benzene, naphthalene, azulene, anthracene, tetracene, pentacene, phenanthrene. , Pyrene, pyrrole, furan, thiophene, pyrazole, imidazole, oxazole, thiazole, triazole, oxadiazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, indole, isoindole, benzoxazole, benzthiazole, benzoisoxazole Benzisothiazole, benzoxadiazole, benzthiadiazole, pyrrolopyridine, pyrrolopyrazine, purine, quinoline, isoquinoline, sinoline, quinazoline, quinoxaline and the like.

  Examples of the substituent of the “substituted or unsubstituted aromatic group” include the same substituents as the substituents of the “substituted or unsubstituted linear or branched alkylene group having 1 to 20 carbon atoms”. .

  The alkyl in the dialkylamino group, alkyloxycarbonyl group, and alkoxy group is a linear or branched alkyl having 1 to 4 carbon atoms, specifically, methyl, ethyl, n-propyl, isopropyl, n -Butyl, s-butyl, t-butyl, isobutyl.

  The “substituted cycloalkyl group having 3 to 7 carbon atoms” of the “substituted or unsubstituted cycloalkylene group having 3 to 7 carbon atoms” is a divalent cyclic alkylene group, specifically, cyclopropylene, cyclobutylene. , Cyclopentylene, cyclohexylene, cycloheptylene and the like.

  The substituent of the “substituted or unsubstituted cycloalkylene group having 3 to 7 carbon atoms” is the same as the substituent of the above “substituted or unsubstituted linear or branched alkylene group having 1 to 20 carbon atoms”. The substituent of this is mentioned.

R ² ′ may be any of the aforementioned groups, but preferably ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, dodecylene, -ethylene-O-ethylene-, -Ethylene-O-ethylene-O-ethylene-, -ethylene-O-ethylene-O-ethylene-O-ethylene-, -ethylene-O-ethylene-O-ethylene-O-ethylene-O-ethylene-, -ethylene -O-ethylene-O-ethylene-O-ethylene-O-ethylene-O-ethylene-, -ethylene-O-propylene-O-ethylene-, -ethylene-O-butylene-O-ethylene-, -ethylene-O -Pentylene-O-ethylene-, -propylene-O-ethylene-O-propylene-, -propylene-O-propylene O-propylene-, -butylene-O-butylene-, and cyclic ethers represented by formula (A), more preferably ethylene, -ethylene-O-ethylene-, -ethylene-O-ethylene-O -Ethylene-,-ethylene-O-ethylene-O-ethylene-O-ethylene-,-ethylene-O-ethylene-O-ethylene-O-ethylene-O-ethylene-,-ethylene-O-ethylene-O-ethylene -O-ethylene-O-ethylene-O-ethylene-, -ethylene-O-propylene-O-ethylene-, -ethylene-O-butylene-O-ethylene-, -ethylene-O-pentylene-O-ethylene-, -Propylene-O-ethylene-O-propylene-, -propylene-O-propylene-O-propylene-, and -butylene-O-butylene- and the formula A), and more preferably ethylene, -ethylene-O-ethylene-, -ethylene-O-ethylene-O-ethylene-, -ethylene-O-ethylene-O-ethylene-O-ethylene. -, -Ethylene-O-ethylene-O-ethylene-O-ethylene-O-ethylene-, and -ethylene-O-ethylene-O-ethylene-O-ethylene-O-ethylene-O-ethylene- and the formula ( A) cyclic ethers represented by A), most preferably represented by -ethylene-O-ethylene-O-ethylene- and -ethylene-O-ethylene-O-ethylene-O-ethylene-, and formula (A) A cyclic ether in which n ⁵ and n ⁶ are 2 or 3.

  The compound represented by the general formula (VIII) may be any compound as long as it satisfies the above-described conditions. Specifically, the following compounds (VIII-1) to (VIII-12) Can be mentioned.

In R ⁴ ′ of formula (IX), “a linear or branched alkyl group having 5 to 20 carbon atoms” of “substituted or unsubstituted linear or branched alkyl group having 5 to 20 carbon atoms” is Specifically, n-pentyl group, 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-methylheptyl group, 2-methylheptyl group, 3-methylheptyl group, 4-methylheptyl 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-dimethylbutane-2 -Yl group, 3-hexyl group, 2-ethylpentyl group, -Methylpentan-3-yl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl Etc.

  As the substituent of the above-mentioned “substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms”, the above “substituted or unsubstituted linear or branched alkylene group having 1 to 20 carbon atoms” is used. It is the same as the substituent of

R ⁴ ′ may be any of the aforementioned groups, but is preferably a heptyl group, an octyl group, a nonyl group, a hydroxyheptyl group, a hydroxyoctyl group, and a hydroxynonyl group, more preferably a heptyl group. , An octyl group, and a nonyl group, and most preferably an octyl group.

  The compound represented by the above formula (IX) may be any compound as long as it satisfies the above-mentioned conditions. Specifically, the following compounds (IX-1) to (IX-3) are listed. be able to.

  When the compounds of formula (VIII) and (IX) have asymmetric carbon atoms, such compounds include all possible optical isomers, which may be in any ratio. For example, an optically active compound may be an enantiomer, a racemate, or an enantiomeric mixture in an arbitrary ratio, and when a plurality of asymmetric points are present, an optically active compound may be an arbitrary ratio of diastereomeric mixtures.

  The compounds represented by the formulas (VIII) and (IX) are obtained by preparing according to the method described in Japanese Patent Application No. 2014-095144.

The sulfur-containing polymer can be synthesized by the following method.
The first step in the synthesis of the sulfur-containing polymer is to melt sulfur by heating in a reaction vessel because sulfur (S ₈ ) is insoluble or difficult to dissolve in an organic solvent. Sulfur has many allotropes (S ₈ and _{S 6, S 12, S 18} , S 20 , etc.), each having a melting point. The most stable allotrope of sulfur is cyclic sulfur (S ₈ ), which has three crystal forms (α sulfur, β sulfur and γ sulfur) with melting points of 112.8 ° C., 119.6 ° C. and 106.8 ° C. Therefore, it is necessary to heat at a temperature of 120 ° C. or higher for melting at least sulfur. Further, sulfur transitions from α-sulfur having a stable structure to β-sulfur, λ-sulfur, and μ-sulfur as the temperature rises, and radical cleavage of cyclic sulfur proceeds at 159.4 ° C. or higher, and a divalent radical is formed. Thus, since sulfur (S ₈ ) generates radicals at a temperature of 159.4 ° C. or higher, the melting temperature must be set lower than the above temperature. The melting temperature of sulfur (S ₈ ) is preferably 120 ° C. to 155 ° C., more preferably 135 ° C. to 155 ° C., further preferably 145 ° C. to 155 ° C., and most preferably 150 ° C. to 155 ° C.

The second stage of the synthesis of the sulfur-containing polymer is radical polymerization of sulfur with a modifying agent having an allyl group represented by formula (VIII) or (IX). Adding the modifier to the molten sulfur prepared in the first step. The temperature at which the modifier is added may be any temperature as long as the sulfur is melted, preferably 130 ° C to 155 ° C, more preferably 135 ° C to 155 ° C, and even more preferably 145 ° C to 155 ° C. Most preferably, it is 150 degreeC-155 degreeC. Since the modifying agent has low homopolymerizability, homopolymerization is not performed, and reaction with sulfur radicals proceeds. Therefore, since sulfur (S ₈ ) generates radicals at a temperature of 159.4 ° C. or higher, the reaction temperature is set to 160 ° C. or higher and the radical polymerization reaction with the modifier is performed. At this time, it is preferable that sulfur and the modifier are uniformly mixed, and the reaction can be performed while stirring. The temperature at which the radical reaction is performed may be any temperature as long as it is 159.4 ° C. or higher, which is the temperature at which sulfur (S ₈ ) generates radicals, but is preferably 160 ° C. to 195 ° C., more preferably 165 ° C. It is -185 degreeC, More preferably, it is 165 degreeC -175 degreeC, Most preferably, it is 165 degreeC-170 degreeC.

  The sulfur-containing polymer synthesized by the above method usually requires no purification work because the reaction proceeds almost quantitatively. However, when a very high-purity sulfur-containing polymer is required, the reaction product is dissolved in an organic solvent using chloroform, N-methyl-2-pyrrolidone, acetonitrile, N, N- By dissolving in dimethylformamide, dimethyl sulfoxide or the like and performing filtration, sulfur insoluble in the organic solvent can be removed. Moreover, it is possible to isolate | separate a polymer and a monomer by using the solution after filtration for molecular sieves, such as a gel filtration chromatography.

  Since the sulfur-containing polymer produced by the above method dissolves in a solvent, NMR measurement is possible. It can also be confirmed by other spectroscopic methods such as IR measurement.

  The above sulfur-containing polymer includes hydrocarbons such as 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; soluble in solvents such as acetonitrile, N, N-dimethylformamide and ethyl acetate.

  The number average molecular weight (Mn) of the sulfur-containing polymer of the present invention is 500 to 10000, preferably 1000 to 5000, and most preferably 1000 to 2000.

In the sulfur-containing polymer of the present invention, the molar ratio of sulfur (S ₈ ) to the compound represented by formula (VIII) or formula (IX) is preferably 1: 0.01 to 1: 100, more preferably. Is 1: 0.05 to 1:20, more preferably 1: 0.5 to 1:10.

  In addition, the sulfur-containing polymer of the present invention has a glass transition temperature, and the glass transition temperature varies greatly depending on the structure of the compound represented by formula (VIII) or formula (IX). The glass transition temperature of the sulfur-containing polymer of the present invention is preferably 40 ° C to -50 ° C, more preferably 30 ° C to -45 ° C, still more preferably -15 ° C to -40 ° C. The glass transition temperature of the sulfur-containing polymer of the present invention can be measured by a well-known technique such as differential scanning calorimetry (DSC).

Among the organic sulfur materials, preferably a diallyl compound selected from compound VIII-7, formula VIII-8, VIII-9, VIII-10, VIII-11 and VIII-12 and molecular sulfur (S ₈ ). It is a sulfur-containing polymer obtained by mixing and heating.

  Furthermore, when forming a positive electrode, the said sulfur-containing polymer can be mixed with a suitable binder and a conductive support agent, and an electrode layer can also be formed. Moreover, the positive electrode of the said magnesium secondary battery can be manufactured by stirring and pressure-bonding the positive electrode material which mixed the sulfur type positive electrode active material of this invention, the conductive support agent, and the binder.

  As the binder, for example, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), styrene-butadiene rubber (SBR), polyimide (PI), polyamideimide (PAI), carboxymethylcellulose (CMC), Polyvinyl chloride (PVC), methacrylic resin (PMA), polyacrylonitrile (PAN), modified polyphenylene oxide (PPO), polyethylene oxide (PEO), polyethylene (PE), polypropylene (PP), polyvinyl alcohol (PVA), etc. It is done. Polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE) are preferable.

  Examples of the conductive assistant include vapor grown carbon fiber (VGCF), carbon powder, carbon black (CB), acetylene black (AB) polypyrrole, polyaniline, ketjen black (KB), graphite, and aluminum. And fine metal powders stable at a positive electrode potential such as titanium and titanium. The conductive assistant is preferably porous carbon, and more preferably ketjen black (KB).

  The weight ratio of the sulfur-containing polymer, the conductive additive (KB) and the binder (PVDF, PTFE) is as follows: The sulfur-containing polymer: conductive auxiliary (KB): binder (PVDF, PTFE) weight ratio = 1-20: 1 to 10: 1 is preferable, and a weight ratio of sulfur-containing polymer: conductive auxiliary agent (KB): binder (PVDF, PTFE) = 5 to 10: 1 to 5: 1 is more preferable.

  The negative electrode of the magnesium secondary battery of the present invention is not particularly limited as long as it is a material capable of occluding and releasing cations, and magnesium is preferable.

  The magnesium secondary battery of the present invention may include a current collector. What is necessary is just to use what is generally used for the positive electrode for secondary batteries as said collector. For example, current collectors include stainless steel foil, stainless steel mesh, aluminum foil, aluminum mesh, punched aluminum sheet, aluminum expanded sheet, stainless steel foil, stainless steel mesh, punched stainless steel sheet, stainless steel expanded sheet, nickel foam, nickel Nonwoven fabric, copper foil, copper mesh, punched copper sheet, copper expanded sheet, titanium foil, titanium mesh, carbon nonwoven fabric, carbon woven fabric, and the like. A stainless mesh is preferred.

  Moreover, in the magnesium 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.

Reference Example 1 Preparation of positive electrode containing sulfur-containing polymer Sulfur-containing polymer was synthesized with reference to Japanese Patent Application No. 2014-095144. When the molar ratio of sulfur (S ₈ ) to the compound represented by VIII-11 in the sulfur-containing polymer is 1: 0.5, sulfur (S ₈ ) (0.5 g, 1.95 mmol) is added to the reaction vessel. The mixture was stirred at 155 ° C. for 10 minutes. After sulfur was dissolved, Compound VIII-11 (0.328 g, 0.39 mmol) obtained by the method described in Japanese Patent Application No. 2014-095144 was added, and the mixture was heated to 160 to 165 ° C. and stirred. Initially, the liquid reaction mixture hardens in about 20 minutes, but the reaction is continued as it is, and a heating reaction is performed at about 160 ° C. for 60 minutes. Furthermore, a yellowish brown rubber-like sulfur-containing polymer was quantitatively obtained by heating to 170 ° C. and stirring. It was Mn = 1600 when the number average molecular weight (Mn) of the polymer was measured by GPC.
The above sulfur-containing polymer (80 mg) (referred to as S-BUMB24C8) was dissolved in chloroform (0.8 g). After confirming dissolution of the polymer, ketjen black (40 mg) was added. After adding polytetrafluoroethylene (PTFE, 13 mg) to this reaction solution, the mixture was pressure-bonded to a current collector to produce an S-BUMB24C8 electrode.

Reference Example 2 Creation of rotaxane network polymer

  The rotaxane network polymer was prepared with reference to International Publication No. 2013/099224 pamphlet. Specifically, a Grubbs catalyst (benzylidenebis (tricyclohexylphosphine) dichlororuthenium, (2.) is added to a dichloromethane solution of the cyclic compound (V-1) (20 mg) and the linear compound (VI-1) (13.8 mg). 0 mg) and stirred for 24 hours at 40 ° C. Ethyl vinyl ether was added and the product was washed several times with dichloromethane and DMF to consist of cyclic compound (V-1) and linear compound (VI-1). A network polymer having a structure in which rotaxane units were polymerized was obtained.

Example 1. Production of Polymer Gel Electrolyte The network polymer obtained in Reference Example 2 was immersed in a 0.7 M Mg (TFSA) ₂ Triglyme solution (2 mL) under an inert gas (nitrogen) atmosphere and left at 60 ° C. for 12 hours. Then, the excess electrolyte solution adhering to the surface of a network polymer was removed using the filter paper, and the gel electrolyte was obtained.

Example 2 Production and Evaluation of Magnesium Secondary Battery Using the polymer gel electrolyte obtained in Example 1, as shown in FIG. 1, the S-BUMB24C8 electrode or vanadium pentoxide produced in Reference Example 1 was used for the positive electrode, and magnesium was used for the negative electrode. The provided magnesium secondary battery was created and charge / discharge measurement was performed. In addition, the positive electrode of vanadium pentoxide was prepared by slurrying vanadium pentoxide (Aldrich), ketjen black, and polyvinylidene fluoride at a weight ratio of 8: 1: 1, and applying the slurry to the current collector. It was prepared by drying.
The charge / discharge measurement results of the magnesium secondary battery using the S-BUMB24C8 electrode or vanadium pentoxide as the positive electrode are shown in FIGS. 2 and 3, respectively.

  The operating temperature of the magnesium secondary battery of the present invention was 25 ° C. The magnesium secondary battery using an organic sulfur material for the electrode had a rate of 0.005 C, a discharge capacity of 350 mAh / g, and a charge / discharge cycle of 10 cycles. The magnesium secondary battery using vanadium pentoxide as an electrode had a rate of 0.001 C, a discharge capacity of 650 mAh / g, and a charge / discharge cycle of one cycle. By using the movement of the ring molecules in the rotaxane network polymer, good charge / discharge was confirmed even in the gel state.

The polymer gel electrolyte of the present invention can prevent the formation of a magnesium metal oxide film on the negative electrode during charging and discharging of a magnesium secondary battery, and can repeatedly perform charging and discharging. Moreover, since the operating temperature of the magnesium secondary battery of this invention operate | moves at room temperature, deterioration of the battery which occurs by the operation | movement at high temperature can be prevented, and a battery with a long lifetime can be obtained. Furthermore, a safe magnesium secondary battery having an effect of preventing liquid leakage can be obtained by using the rotaxane network polymer as the magnesium-based gel electrolyte.

Claims (6)

(1) Formula (I)
Wherein R ¹ and R ² are the same or different and may have —O—, —CO—, —COO—, or —CONH—, saturated or partially unsaturated, linear or branched In the cyclic part of the partial structure represented by the chain, a hydrocarbon group having 1 to 15 carbon atoms, n1 represents an integer of 3 or 4. n2 represents an integer of 1 to 30.
Formula (II)
Wherein R ³ and R ⁴ are the same or different and may have —O—, —CO—, —COO— or —CONH—, saturated or partially unsaturated, linear or branched Represents a hydrocarbon group having 1 to 15 carbon atoms in the chain, and Z ⁻ represents a counter anion.), Or Formula (II ′)
(Wherein R ³ and R ⁴ are the same as defined in formula (II), and R ⁵ represents a residue derived from an electrophile), and the partial structure represented by skewering is included. A polymer comprising a rotaxane network polymer having a unit (A) or an electrolyte solution containing the unit (A) and a rotaxane network polymer having a unit (B) derived from a radical polymerizable monomer and (2) a magnesium salt Gel electrolyte. (1) The unit (A) of the rotaxane network polymer is
Formula (III)
(In the formula, m is an integer of 1 to 13, and the dotted line part indicates that it is bonded to either the 3-position or the 4-position of the benzene ring. N2 represents an integer of 1 to 30). In the annular part of the partial structure
Formula (IV)
2. The unit according to claim 1, wherein the partial structure represented by the formula (wherein y represents an integer of 1 to 12 and Z ⁻ represents a counter anion) is included in a skewered manner. Polymer gel electrolyte. The polymer gel electrolyte according to claim 1 or 2, wherein the electrolyte solution containing magnesium salt is a triethylene glycol dimethyl ether (Triglyme) solution of Mg (TFSA) ₂ .   A magnesium secondary battery using the electrolyte according to claim 1.   The magnesium secondary battery according to claim 4, wherein the positive electrode is an organic sulfur material or vanadium pentoxide, and the negative electrode is magnesium metal.   The magnesium secondary battery according to claim 5, wherein the positive electrode is a sulfur-containing polymer.