JP6486143B2 - Sulfur-containing polymer - Google Patents

Description

The present invention relates to a sulfur-containing polymer which is a novel network polymer obtained by reacting solid sulfur (S ₈ ) and an allyl compound, and also relates to an elastomer containing the sulfur-containing polymer and a battery material containing the sulfur-containing polymer. .

As for the use of surplus sulfur recovered during petroleum refining, there are various uses such as industrial chemicals such as sulfuric acid, additives such as rubber, and fertilizers. However, since sulfur is not used as a main component in these applications, the amount of sulfur consumed does not keep up with the production amount, and it is a problem that a large amount of money is required for storing surplus sulfur. Therefore, techniques for physical properties change due to chemical modifications in order to expand applications of solid sulfur S ₈ have been reported in some decade.

  Patent Document 1 describes a method for producing sulfur-modified polyacrylonitrile by reacting polyacrylonitrile and solid sulfur for use as a battery material. However, the method for producing the sulfur-modified polyacrylonitrile has a problem that harmful hydrogen sulfide gas is generated and the quality of the produced sulfur-modified polyacrylonitrile varies greatly depending on the quality of the raw material polyacrylonitrile. ing.

  Patent Document 2 reports the synthesis of an organic sulfur polymer having a high sulfur content by radical polymerization of polyisoprene and solid sulfur for use as a secondary battery material. However, even in the method for producing the organic sulfur polymer, harmful hydrogen sulfide gas is generated, and it is necessary to use an excessive amount of sulfur with respect to polyisoprene. It has a problem that it needs to be removed.

  Patent Document 3 describes a polysulfide carbon composed of a reaction between a halogenated unsaturated hydrocarbon such as hexachlorobutadiene and sulfur for use as a positive electrode material of a secondary battery material, and a method for producing the same. However, in the above production method, there is a problem that sulfur needs to be reacted with an alkali metal sulfide such as sodium sulfide, and the production of polysulfide carbon requires a multi-step process. In addition, the polysulfide carbon has no or very low solubility in an organic solvent, and there remains a problem regarding material handling.

  In addition, for use as a building material or a paving material, Patent Document 4 reports the synthesis of an organic sulfur polymer having a high sulfur content by radical polymerization of a double bond such as ethylidene norbornene and solid sulfur. However, the structure of the modifier having these double bonds is limited, and the physical properties cannot be diversified. Moreover, since the solubility with respect to an organic solvent is also poor, the subject remains regarding handling of a material.

Further, Non-Patent Document 1 describes a copolymer of an active vinyl compound such as 1,3-diisopropenylbenzene and α-methylstyrene and sulfur (S ₈ ). However, since this active vinyl compound has a very high radical polymerizability, it causes self-polymerization in addition to the reaction with sulfur, and the copolymer loses uniformity. Moreover, when a small amount of an active vinyl compound is used, the solubility of the copolymer in an organic solvent cannot be imparted.

  Patent Document 5 is a patent document by the same group as the author of Non-Patent Document 1, and is a co-polymerization of sulfur and one or more ethylenically unsaturated monomers, epoxide monomers, or thiirane monomers, or combinations thereof. Coalescence is described. It is described that the copolymer can be used as an electrochemical cell or an optical material. However, since the ethylenically unsaturated monomer has a very high radical polymerizability, it causes self-polymerization in addition to the reaction with sulfur, and the copolymer loses uniformity. In addition, the epoxide monomer or thiirane monomer has a problem that it is necessary to use an onium salt such as tetraphenylphosphine chloride which is unnecessary after the polymerization in the reaction.

WO2010 / 044437 JP 2012-150933 A JP 2003-123758 A WO2007 / 055351 WO2013 / 023216

Nature Chemistry, Vol. 5, p. 518-524 (2013).

  The present invention has been made in view of such circumstances, and in order to obtain a novel organic sulfur material having elasticity and solubility, it has high solubility and uniformity in an organic solvent having a high sulfur content. It aims at obtaining the new sulfur-containing polymer which has.

As a result of intensive studies to solve the above problems, the present inventors have found that a network polymer having high uniformity obtained by radical reaction of a monomer having an allyl group and sulfur (S ₈ ) with respect to an organic solvent. It has been found that it has excellent solubility and also has excellent elasticity, and has completed the present invention.

That is, the present invention provides (1) Formula (I)

[In formula (I), R ¹ and R ³ are each independently
A linking group represented by -COO-, -OCO-, -CONH-, -NHCO-, or -O-, a substituted or unsubstituted linear or branched alkylene group having 1 to 20 carbon atoms, and a linking group; A substituted or unsubstituted linear or branched carbon number having any one or two selected from the group consisting of —COO—, —OCO—, —CONH—, —NHCO—, and —O— as a group Represents any one selected from the group consisting of 1 to 19 alkylene groups;
R ² represents a substituted or unsubstituted linear or branched alkylene group having 2 to 20 carbon atoms,
A substituted or unsubstituted linear or branched alkylene group having 2 to 20 carbon atoms, a substituted or unsubstituted aromatic group, a substituted or unsubstituted carbon number of 3 to 7 having one or more —O— in the main chain A cycloalkylene group of the formula

(In the formula, n ⁵ and n ⁶ are each independently an integer of 1 to 4,
The bond represented by the broken line represents any one selected from the group consisting of groups represented by the formula (II) or the formula (II)

(Wherein R ⁴ represents a substituted or unsubstituted linear or branched alkyl group having 5 to 20 carbon atoms);
A sulfur-containing polymer obtained by mixing and heating with molecular sulfur (S ₈ ),
(2) The diallyl compound represented by the formula (I) is represented by the following formula (III)

(In the formula, n ¹ and n ³ are each independently an integer of 0 to 19,
n ² is an integer of 1 to 10. The sulfur-containing polymer according to (1) above, which is a compound represented by
(3) A diallyl compound represented by formula (I) is represented by the following formula (V):

(Wherein n ⁴ and n ⁷ are each independently an integer of 0 to 19,
n ⁵ and n ⁶ are each independently an integer of 1 to 4,
The sulfur-containing polymer as described in (1) above, wherein the broken-line bond represents a compound represented by the bond at the 3-position or 4-position of the benzene ring),
(4) The sulfur-containing polymer according to any one of (1) to (3) above, wherein the heating is from 155 to 170 ° C,
(5) The molar ratio of sulfur to the compound represented by formula (I) or formula (II) is from 1: 0.01 to 1: 100, wherein the above (1) to (4) The sulfur-containing polymer according to any one of the above.

Furthermore, the present invention provides
(6) A battery material containing the sulfur-containing polymer according to any one of (1) to (5) above,
(7) The battery material according to (6) above, which is used for a positive electrode of a secondary battery including a primary battery or a polyvalent cation battery,
(8) The battery material according to (7) or (9) the secondary battery is magnesium, wherein the negative electrode of the secondary battery is any one selected from lithium, magnesium, aluminum, and sodium. The battery material according to (7) above, which is a secondary battery,
(10) A magnesium secondary battery comprising the battery material according to (9) above.

Since the novel sulfur-containing polymer of the present invention has excellent solubility in an organic solvent, sulfur (S ₈ ) and a modifier can be kneaded in a uniform and free blending ratio as compared with conventional organic sulfur polymers. Therefore, processing became easy. As a result, it is possible to prepare an electrode material uniformly kneaded with the sulfur-containing polymer of the present invention and a conductive additive, and to suppress the elution of polysulfide ions (sulfur components) even if the reaction cycle is repeated. It became clear from the evaluation. In addition, since the sulfur-containing polymer of the present invention has high elasticity, it can be used as an elastomer or rubber material in the construction and automobile industries. Furthermore, the sulfur-containing polymer of the present invention is excellent as a positive electrode material for a magnesium secondary battery, and can be used for a magnesium secondary battery.

2 is a diagram illustrating a ¹ H-NMR spectrum of a sulfur-containing polymer of Production Example 1 in deuterated chloroform. FIG. It is a figure showing the ¹³ C-NMR spectrum in the heavy chloroform of the sulfur-containing polymer of manufacture example 1. It is a figure showing the measurement result by DSC of the sulfur-containing polymer of manufacture example 1. It is a figure showing the measurement result by SEM-EDS of the sulfur-containing polymer of manufacture example 1. It is a figure showing the measurement result by the cyclic voltammetry (CV) of the electrode material manufactured in Example 2. FIG. 6 is a diagram illustrating a structure of a magnesium secondary battery manufactured in Example 4. FIG. It is a figure showing the result of the charging / discharging measurement of the magnesium secondary battery produced in Example 4. FIG.

The sulfur-containing polymer of the present invention 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 has the following formula (I ) Or (II) (hereinafter referred to as compound (I) or (II). The same applies to compounds of other formula numbers).

(Diallyl compound)
The diallyl compound is a compound represented by the following formula (I):

[In Formula (I), R ¹ and R ³ each independently represent a linking group represented by —COO—, —OCO—, —CONH—, —NHCO—, or —O—, substituted or unsubstituted. A linear or branched alkylene group having 1 to 20 carbon atoms and any one selected from the group consisting of —COO—, —OCO—, —CONH—, —NHCO—, and —O— as a linking group. One or two substituted or unsubstituted linear or branched alkylene groups having 1 to 19 carbon atoms,
R ² represents a substituted or unsubstituted linear or branched alkylene group having 2 to 20 carbon atoms, a substituted or unsubstituted linear or branched carbon atom having 2 or more —O— in the main chain. 20 alkylene groups, substituted or unsubstituted aromatic groups, substituted or unsubstituted cycloalkylene groups having 3 to 7 carbon atoms, and the following formula:

(In the formula, n ⁵ and n ⁶ are each independently an integer of 1 to 4,
The broken-line bond represents any one selected from the group consisting of groups represented by the following):
It is.

In the above formula (I), R ¹ and R ³ are each independently a linking group represented by —COO—, —OCO—, —CONH—, —NHCO—, or —O—, substituted or unsubstituted. A linear or branched alkylene group having 1 to 20 carbon atoms and any one selected from the group consisting of —COO—, —OCO—, —CONH—, —NHCO—, and —O— as a linking group. Or a substituted or unsubstituted straight chain or branched alkylene group having 1 to 19 carbon atoms.

  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. And a group bonded to R ² , specifically, in the relationship with an allyl group and R ² , allyl group-alkylene group-COO-R ² , allyl group-alkylene group-OCO-R ² , allyl group- Alkylene group -CO ^{H-R 2,} allyl group - alkylene group ^{-NHCO-R 2,} allyl group - alkylene group ^{-O-R 2,} allyl group -COO- alkylene group -R ^2, an allyl group -COO- alkylene group ^{-COO-R 2} , allyl group -COO- alkylene group ^{--OCO-R 2,} allyl group -COO- alkylene group ^{-CONH-R 2,} allyl group -COO- alkylene group ^{-NHCO-R 2,} allyl group -COO- alkylene group -O- R ² , allyl group-OCO-alkylene group-R ² , allyl group-OCO-alkylene group-COO-R ² , allyl group-OCO-alkylene group-OCO-R ² , allyl group-OCO-alkylene group-CONH- R ^2, an allyl group -OCO- alkylene group ^{-NHCO-R 2,} allyl group -OCO- alkylene group ^{-O-R 2,} allyl group -CONH- al Ren group -R ^2, an allyl group -CONH- alkylene group ^{-COO-R 2,} allyl group -CONH- alkylene group ^{-OCO-R 2,} allyl group -CONH- alkylene group ^{-CONH-R 2,} an allyl group -CONH- Alkylene group-NHCO-R ² , allyl group-OCO-alkylene group-O-R ² , allyl group-NHCO-alkylene group-R ² , allyl group-NHCO-alkylene group-COO-R ² , allyl group-NHCO- alkylene group ^{-OCO-R 2,} allyl group -NHCO- alkylene group ^{-CONH-R 2,} allyl group -NHCO- alkylene group ^{-NHCO-R 2,} 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- alkylene group -CONH- ^2, an allyl group -O- alkylene group ^{-NHCO-R 2,} represented by an allyl group -O- alkylene group ^{--OCO-R 2,} and allyl group -O- alkylene group ^{-O-R 2.}
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 above-mentioned 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 R in relation to the ^2, allyl group - hexylene ^{-COO-R 2,} an allyl group - heptylene ^{COO-R 2,} and allyl groups - an octylene ^{-COO-R 2.}

In the above formula (I), R ² represents a substituted or unsubstituted straight chain or a branched alkylene group having 2 to 20 carbon atoms, a substituted or unsubstituted straight chain having one or more —O— in the main chain, or A branched alkylene group having 2 to 20 carbon atoms, a substituted or unsubstituted aromatic group, a substituted or unsubstituted cycloalkylene group having 3 to 7 carbon atoms, and a cyclic ether moiety represented by the following formula 1a;

[Wherein n ⁵ and n ⁶ are each independently an integer of 1 to 4,
The bond of the broken line represents a bond to the 3-position or 4-position of the benzene ring] is selected from the group consisting of groups represented by

The above-mentioned “substituted or unsubstituted straight chain or branched alkylene group having 2 to 20 carbon atoms” is the substituted or unsubstituted straight chain or branched carbon number 1 to 20 shown in R ¹ and R ^3. The same thing as the alkylene group of 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 or branched alkylene of 2 to 20 carbon _atoms) m1 ^-R 3,
R ^1- (straight chain or branched alkylene having 2 to 20 carbon atoms) _{m 1} -R ³ ,
R ¹ - (O-straight or branched alkylene of 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) _m 2 —R ³ ,
R ¹ - (linear or branched alkylene -O 2 to 20 carbon _{atoms) m @ 2} - alkylene -R ³ or the like having 2 to 20 carbon atoms of straight or branched may be mentioned.

“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 is 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, and -butylene-O-butylene-, and cyclic ethers represented by Formula 1a, 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 formula 1a 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 represented by Formula 1a And most preferably -ethylene-O-ethylene-O-ethylene- and -ethylene-O-ethylene-O-ethylene-O-ethylene-, and the cyclic ether of formula 1a, n ⁵ and n ⁶ is a cyclic ether having 2 or 3;

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

(Monoallyl compound)
As the monoallyl compound, a compound represented by the following formula (II):

[In formula (II), R ⁴ represents a substituted or unsubstituted linear or branched alkyl group having 5 to 20 carbon atoms].

  The “straight or branched alkyl group having 5 to 20 carbon atoms” of the “substituted or unsubstituted linear or branched alkyl group having 5 to 20 carbon atoms” specifically includes an 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-dimethylbutan-2-yl group, 3-hexyl group, 2-ethylpentyl group, 2-methylpentane-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 preferably heptyl group, octyl group, nonyl group, hydroxyheptyl group, hydroxyoctyl group, and hydroxynonyl group, more preferably heptyl group, An octyl group and a nonyl group, most preferably an octyl group.

  The compound represented by the general formula (II) may be any compound as long as it satisfies the above conditions. Specifically, the following compounds (II-1) to (II-3) Can be mentioned.

  When the compounds represented by general formulas (I) and (II) 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.

(Method for producing allyl compound)
Although the example of the manufacturing method of the compound represented by the said general formula (I) and (II) is demonstrated below, it is not limited to these manufacturing methods, Moreover, the compound which can be obtained as a commercial item also includes is there.

The site | part represented by R < ¹ > or R < ³ > of the said general formula (I) can be prepared, for example from a secoic acid. As shown in the following formula, by reacting secocic acid in an alcohol under an acid condition, an ester of secocic acid can be obtained (wherein the wavy line represents methylene having 2 to 12 carbon atoms. The same applies hereinafter. .) As the acid, sulfuric acid, methanesulfonic acid, paratoluenesulfonic acid, camphorsulfonic acid and the like can be used. As the alcohol, it is preferable to use a primary alcohol such as methanol or ethanol. The reaction can be performed at any temperature from room temperature to the boiling point of the reaction solution. Next, the primary alcohol portion of the obtained ester of secoic acid is oxidized to prepare an aldehyde. As the oxidation reaction of the primary alcohol, known methods such as Dess-Martin oxidation, SO ₃ -pyridine oxidation, and TEMPO oxidation can be used. R ¹ or R ³ having an allyl moiety can be adjusted by converting the obtained aldehyde into an olefin by a Wittig reaction. The resulting compound can be prepared from (i) a carboxylic acid having an allyl moiety by a hydrolysis reaction and (ii) an alcohol having an allyl moiety by a reduction reaction. As the hydrolysis reaction, an alkali such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydroxide, potassium hydroxide, lithium hydroxide, etc. in a water-containing solvent such as ethanol, tetrahydrofuran, dimethylacetamide, The method of making it react at the temperature between 0 degreeC and the boiling point of a solvent can be mentioned. Examples of the reduction reaction include a method in which sodium borohydride is allowed to act in an alcohol solvent such as methanol and ethanol, and a method in which a reducing agent such as lithium aluminum hydride and diisopropylaluminum hydride is allowed to act in tetrahydrofuran. it can.

Moreover, the site | part represented by R < ¹ > or R < ³ > of the said general formula (I) can be prepared from allyl alcohol and a secoic acid. An alcohol having an allyl moiety can be prepared by esterifying allyl alcohol and secoic acid with a hydroxyl group protected and deprotecting the protecting group of the resulting ester. Protection and deprotection of hydroxyl groups, Green & Wuts, "PROTECTIVE GROUPS in ORGANIC SYNTHESIS" 3 rd ed.John Wiley & Sons, can refer to Inc., PG in the formula, for example, tert- butyldimethylsilyl group, a methyl group, Protecting groups such as methoxymethyl group, benzyl group, acetyl group and the like are represented. Examples of the esterification include a reaction in which a carbodiimide-based condensing agent such as dicyclohexylcarbodiimide or WSCI is reacted between room temperature and the boiling point of the reaction solution in a solvent such as dichloromethane, toluene, N, N-dimethylacetamide. it can. In the reaction, pyridine, dimethylaminopyridine, 4-pyrrolidinopyridine or the like may be used as a catalyst. A carboxylic acid having an allyl moiety can be prepared by oxidizing the alcohol having an allyl moiety obtained by the above-described method into an aldehyde by the above-described oxidation reaction and then performing Pinnick (Kraus) oxidation.

Furthermore, moiety represented by R ¹ or R ³ in the above general formula (I) can be prepared from 3-butenoic acid and a diol. Alcohol having an allyl moiety can be prepared by esterifying 3-butenoic acid and secoic acid in which one hydroxyl group is selectively protected, and deprotecting the protecting group of the resulting ester. As the esterification, the same method as described above can be used. The protection and deprotection of hydroxyl groups, Green & Wuts, "PROTECTIVEGROUPS in ORGANIC SYNTHESIS" 3 rd ed.John Wiley & Sons, can refer to Inc., PG in the formula, for example, tert- butyldimethylsilyl group, a methyl group Represents a protecting group such as a methoxymethyl group, a benzyl group, and an acetyl group. The carboxylic acid having an allyl moiety can be prepared from the alcohol having an allyl moiety obtained by the above-described process by the aforementioned process.

Moiety represented by R ² in the above general formula (I) can be used diol, a dicarboxylic acid. Further, when R ² is linked to R ¹ or R ³ by a single bond, the diol moiety can be converted to a leaving group and linked to R ¹ or R ³ . Examples of the leaving group include tosyl group, bromine, iodine and the like. Examples of the method for converting a hydroxyl group to a leaving group include a method in which diol is reacted with tosyl chloride at 0 ° C. to room temperature in dichloromethane in the presence of an organic base such as triethylamine or diisopropylethylamine. A method for obtaining a dihalo compound by reacting the thus obtained ditosyl ester with potassium bromide, sodium bromide, potassium iodide, or sodium iodide under heating and refluxing in acetone can be mentioned. Diols can also be converted directly into dihalo compounds by the Appel reaction.

Moiety represented by R ² in the above general formula (I), when a polyether can be prepared using a diol. A halide is prepared by the reaction shown above with a diol selectively protecting one hydroxyl group (wherein X represents bromine or iodine). The halide and a diol selectively protecting one of the hydroxyl groups are condensed by a Williamson etherification reaction to obtain an ether. After selective removal of the protecting group, the hydroxyl group is converted to halogen. The resulting compound is further condensed with a diol selectively protecting one of the hydroxyl groups by a Williamson etherification reaction to obtain an ether. By continuing this sequentially, a polyether can be synthesized. Subsequent removal of the protecting group allows conversion to a diol. The hydroxyl group of the diol can be converted to the leaving group E. In the formula, examples of E include a tosyl group, bromine and iodine. The protection and deprotection of hydroxyl groups, Green & Wuts, "PROTECTIVE GROUPS in ORGANIC SYNTHESIS" 3 rd ed.John Wiley & Sons, can refer to ^{Inc., PG 1, PG 2,} PG 3 in the formula, for example tert -Represents protecting groups such as butyldimethylsilyl, methyl, methoxymethyl, benzyl and acetyl groups.

Moiety represented by R ² in the above general formula (I), when a cyclic ether represented by Formula 1a, wherein the cyclic ethers may be prepared by the following method. One hydroxyl group of ethylene glycol (n = 1), diethylene glycol (n = 2), or triethylene glycol (n = 3) is selectively tosylated, and this is 3,4-dihydroxy in the presence of a catalytic amount of acid. A dipolyether of benzoic acid is prepared by condensation reaction of benzoic acid with alcohol under heating and reflux. The tosylation reaction can be carried out under the aforementioned conditions. Examples of the alcohol used as the reaction solvent include ethanol, n-propanol, and isopropanol. Examples of the acid as the catalyst include sulfuric acid, methanesulfonic acid, toluenesulfonic acid, camphorsulfonic acid and the like. Subsequently, the terminal hydroxyl group of the dipolyether of benzoic acid can be tosylated and condensed with 3,4-dihydroxybenzoic acid again to synthesize a cyclic ether (in the formula, the dotted line indicates the 3-position or 4-position of the benzene ring). ). The obtained cyclic ether moiety can be converted into a carboxylic acid, an alcohol, or a leaving group E (E represents a tosyl group, bromine, iodine or the like) by the above-described method.

When R ¹ , R ² , and R ³ obtained by the above method are linked, the ester bond can be linked by the same method as the method using the above-mentioned carbodiimide condensing agent. When R ¹ or R ³ and R ² are linked by an ether bond, they can be linked by a Williamson etherification reaction.

Further, when R ¹ or R ³ and R ² are linked by a carbon-carbon bond, the hydroxyl group of each alcohol of R ¹ and R ³ synthesized above is a leaving group E ¹ (E ¹ is a tosyl group) shown below. Can be linked to each other by reacting with an anionic compound derived from the R ² site.

As shown below, the anion compound derived from the R ² site is a compound having a leaving group E in an organic solvent such as diethyl ether or tetrahydrofuran at −78 ° C. to 0 ° C. with an organic lithium reagent or metallic lithium. It can prepare by making it react with. The anionic compound thus obtained can be linked to the compound having the leaving group E ¹ as it is or by a coupling reaction using a copper salt such as copper bromide, copper iodide, or copper cyanide as a catalyst. .

  The compound represented by the general formula (II) can be synthesized by oxidizing a primary alcohol into an aldehyde in the same manner as described above, and then converting it into an olefin by a Wittig reaction.

(Sulfur-containing polymer)
The sulfur-containing polymer of the present invention 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 modifier having an allyl group represented by formula (I) or (II). 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, tetrahydrofuran, etc. 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.

  Although the structure of the network polymer produced by the above method is a sulfur-containing polymer, it dissolves in a solvent, so NMR measurement, GPC (gel permeation chromatography) measurement, MALDI (matrix-assisted laser desorption ionization) Method) / TOFMS (time-of-flight mass spectrometer) measurement. It can also be confirmed by other spectroscopic methods such as IR measurement.

  The sulfur-containing polymer of the present invention 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; 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 300 to 10000, preferably 1000 to 5000, and most preferably 1000 to 2000. The number average molecular weight (Mn) of the sulfur-containing polymer of the present invention can be measured by GPC.

In the sulfur-containing polymer of the present invention, the molar ratio of sulfur (S ₈ ) to the compound represented by formula (I) or formula (II) 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 (I) or formula (II). 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 20 ° 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).

The sulfur-containing polymer of the present invention can be used as a battery material. When used as a battery material, the sulfur material and the conductive additive can be kneaded in a uniform and free blending ratio due to excellent solubility in an organic solvent, so that the battery material can be easily prepared and processed. Moreover, the battery material of this invention can be used for the secondary battery containing a primary battery or a polyvalent cation battery. In particular, the battery material is preferably used for a positive electrode of a magnesium secondary battery.
Further, the curing reaction can be performed by hot pressing the sulfur-containing polymer of the present invention. As a result, elution of polysulfide ions (sulfur components) can be suppressed even when many reaction cycles are repeated in electrochemical evaluation.

  Moreover, it is preferable that the battery material of this invention contains the conductive support agent and the binder in addition to the sulfur-containing polymer of this invention. For example, the positive electrode of the magnesium secondary battery can be produced by stirring and pressure-bonding a positive electrode material obtained by mixing the sulfur-based positive electrode active material of the present invention, a conductive additive, and a binder.

  Examples of the conductive assistant include vapor grown carbon fiber (VGCF), carbon powder, carbon black (CB), acetylene black (AB), ketjen black (KB), graphite, aluminum, titanium, and the like. Metal fine powder stable at the positive electrode potential. The conductive assistant is preferably porous carbon, and more preferably ketjen black (KB).

  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.

  Weight ratio of sulfur-containing polymer, conductive auxiliary (KB) and binder (PVDF, PTFE) to be blended (sulfur-containing polymer: conductive auxiliary (KB): binder (PVDF, PTFE) is 1 to 20: 1 to 10 : 1 is preferable, and 5 to 10: 1 to 5: 1 is more preferable.

  In the secondary battery using the sulfur-containing polymer of the present invention, the negative electrode is preferably any one selected from lithium, magnesium, aluminum, and sodium, and more preferably magnesium.

  What is necessary is just to use what is generally used for the positive electrode for secondary batteries as a collector used for the secondary battery using the sulfur-containing polymer of this invention. 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.

  The electrolyte used for the secondary battery using the sulfur-containing polymer of the present invention is 1,2-dimethoxyethane, acetonitrile, propylene carbonate, ethylene carbonate, 3-methoxypropionitrile, methoxyacetonitrile, ethylene glycol, propylene glycol, deethylene. Glycol, triethylene glycol, butyrolactone, dimethoxyethane, dimethyl carbonate, 1,3-dioxolane, methyl formate, 2-methyltetrahydrofuran, 3-methoxyoxazolidene-2-one, sulfolane, tetrahydrofuran , Triethylene glycol dimethyl ether (Triglyme), water, and the like. In particular, triethylene glycol dimethyl ether (Triglyme) is preferable. These can be used alone or in combination.

Moreover, the electrolyte used for the secondary battery using the sulfur-containing polymer of the present invention contains lithium bis (trifluoromethanesulfonyl) amide (LiTFSA), magnesium bis (trifluoromethanesulfonyl) amide [Mg (TFSA) ₂ ], and the like. Is preferred. In particular, magnesium bis (trifluoromethanesulfonyl) amide [Mg (TFSA) ₂ ] is preferable.

When the battery material containing the sulfur-containing polymer of the present invention is used as a positive electrode material for a magnesium secondary battery, metallic magnesium is used for the negative electrode of the magnesium secondary battery, and a Triglyme solution of Mg (TFSA) ₂ is used for the electrolyte. it can.

  Moreover, there is no restriction | limiting in particular about the shape etc. of the secondary battery containing the primary battery containing the sulfur-containing polymer of this invention, or a polyvalent cation battery. 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.

  Furthermore, since the sulfur-containing polymer of the present invention has high elasticity, it can be applied to elastomers and rubber materials in the construction and automobile industries.

  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.

Example 1. Synthesis of sulfur-containing polymers

[Production Example 1]
In sulfur-containing polymer, the molar ratio of the compound represented by the sulfur _{(S 8)} and formula (I) is 1: When 0.2, the reaction vessel sulfur _{(S 8) (0.5g, 1.95mmol} ) And stirred at 155 ° C. for 10 minutes. After sulfur was dissolved, Compound I-11 (0.328 g, 0.39 mmol) 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 = 1400 when the number average molecular weight (Mn) of the polymer was measured by GPC. A ¹ H-NMR spectrum of the polymer in deuterated chloroform is shown in FIG. 1, and a ¹³ C-NMR spectrum is shown in FIG.

  Compound I-11 was synthesized with reference to the synthesis procedure described in International Publication No. 2013/099224 pamphlet. Specifically, it was synthesized by the following procedure.

Synthesis of triethylene glycol monotosylate Triethylene glycol (90.6 g, 0.600 mol), 4- (dimethylamino) pyridine (0.147 g, 1.21 mmol), and triethylamine (50.4 mL, 0.362 mol). Dissolved in THF (120 mL), a solution of p-toluenesulfonyl chloride (23.0 g, 0.121 mol) in THF (100 mL) was added. Stir at room temperature for 23 hours, filter the reaction mixture and concentrate the filtrate. The residue was purified by column chromatography to obtain triethylene glycol monotosylate (30.0 g, 81%).

Synthesis of ethyl 3,4-dihydroxybenzoate A mixture of 3,4-dihydroxybenzoic acid (8.0 g, 0.052 mol) and a catalytic amount of p-toluenesulfonic acid was dissolved in ethanol and refluxed for 6 days. The solvent was removed under reduced pressure, and the residue was dissolved in ethyl acetate and washed with water. The solvent was distilled off from the organic layer to obtain ethyl 3,4-dihydroxybenzoate (8.43 g, 89%).

Synthesis of 4-ethyl-1,2-bis [2- [2- (2-hydroxyethoxy) ethoxy] ethoxy] benzoate Ethyl 3,4-dihydroxybenzoate (8.0 g, 0.040 mol), triethylene glycol monotosy The rate (29.4 g, 0.097 mol) and potassium carbonate (15.3 g, 0.10 mol) were dissolved in acetone (240 mL) and heated to reflux for 17 hours. The solution was filtered and the filtrate was concentrated. The target product (15.0 g, 76%) was obtained by purification by column chromatography.

Synthesis of 4-ethyl-1,2-bis [2- [2- [2-[(4-toluene) sulfonyl] oxy] ethoxy] ethoxy] ethoxy] benzoate 4-ethyl-1,2-bis [2- [ 2- (2-hydroxyethoxy) ethoxy] ethoxy] benzoate (15.0 g, 33.6 mol), 4- (dimethylamino) pyridine (0.082 g, 0.67 mmol), and triethylamine (14.1 mL, 100.0 mmol) ) Was dissolved in THF (80 mL), and a solution of p-toluenesulfonyl chloride (19.2 g, 100.0 mmol) in THF (50 mL) was added. Stir at room temperature for 165 hours, filter the reaction mixture and concentrate the filtrate. The residue was purified by column chromatography to obtain the desired product (22.6 g, 89%).

Synthesis of bis (ethoxycarbonylbenzo) -24-crown-8-ether 4-ethyl-1,2-bis [2- [2- [2-[(4-toluene) sulfonyl] oxy] ethoxy] ethoxy] ethoxy] A suspension of benzoate (7.5 g, 9.9 mmol) and cesium carbonate (16.1 g, 49.5 mmol) in acetonitrile (400 mL) was stirred at 60 ° C. for 30 minutes. Thereafter, a solution of ethyl 3,4-dihydroxybenzoate (1.61 g, 8.91 mmol) in THF (100 mL) was added dropwise and heated to reflux for 100 hours. The suspension was filtered and the filtrate was concentrated under reduced pressure. The residue was extracted with dichloromethane and dried over magnesium sulfate. The target product was obtained by distilling off the solvent and purifying by column chromatography (2.99 g, 57%).

Synthesis of bis (hydroxymethylbenzo) -24-crown-8-ether To a THF suspension of lithium aluminum hydride (2.25 g, 59.3 mmol) was added bis (ethoxycarbonylbenzo) -24-crown-8-ether. A solution of (2.93 g, 4.94 mmol) was added and refluxed for 60 hours. Saturated aqueous sodium hydrogen carbonate solution was added at room temperature. The reaction solution was filtered and the filtrate was extracted with dichloromethane. The organic layer was dried over magnesium sulfate and distilled under reduced pressure to obtain the desired product (2.47 g, 98%).

Synthesis of bis (undecenoyloxymethyl) -24-crown-8-ether (I-11) Bis (hydroxymethylbenzo) -24-crown-8-ether (2.46 g 4.84 mmol) was dissolved in THF, Triethylamine (2.70 mL, 19.4 mmol) was added. A THF solution of 10-undecenoyl chloride (3.30 g, 16.3 mmol) was added dropwise. The mixture was stirred at room temperature for 48 hours, and saturated aqueous sodium hydrogen carbonate solution was added. Extraction was performed with dichloromethane, and the organic layer was dried over magnesium sulfate. The concentrated residue was purified by column chromatography to obtain the target compound I-11 (2.78 g, 68%).

  When the glass transition temperature of the polymer obtained in Production Example 1 was measured by DSC, a glass transition temperature of −2.0 ° C. was confirmed. The melting point was 119.4 ° C. As for sulfur, an endothermic peak due to α → β transition is observed at around 100 ° C. However, since the peak was not confirmed in the polymer obtained in Production Example 1, it is considered that sulfur does not remain in the polymer. FIG. 3 shows the measurement results.

  Further, as a result of mapping the composition of the polymer obtained in Production Example 1 with a scanning electron microscope (SEM) and characteristic X-ray measurement (energy dispersive X-ray measurement: EDS), sulfur atoms are uniformly contained in the polymer. It turns out that it is distributed. The measurement result of SEM-EDS is shown in FIG.

[Production Examples 2 to 8]
Under the same conditions as in Production Example 1, the type of the compound represented by Formula (I) and the molar ratio with sulfur were changed to obtain polymers of Production Examples 2-8. In addition, I-8, I-2, and I-5, which are monomer compounds represented by the formula (I), were synthesized by the following procedure.

(Synthesis of Monomer Compound I-8)

Synthesis of bis (formylbenzo) -18-crown-6-ether Dibenzo-18-crown-6-ether (2.0 g, 5.55 mmol) and hexamethylenetetramine (3.89 g, 27.8 mmol) and trifluoroacetic acid (12 ml) was added and the mixture was heated and stirred at 80 ° C. for 27 hours. Then, it cooled to room temperature, distilled water (3 ml) was added, and it stirred for 40 hours. Extraction was performed with chloroform, and the organic layer was dried and concentrated with magnesium sulfate to obtain a product (2.30 g, 100%).

Synthesis of bis (hydroxymethylbenzo) -18-crown-6-ether Bis (formylbenzo) -18-crown-6-ether (2.30 g, 5.52 mmol) was mixed with 200 ml of a methanol / dichloromethane mixture (1: 3). Of sodium borohydride (0.84 g, 22.1 mmol) was added and refluxed for 46 hours. After the reaction, distilled water (100 ml) was added while cooling with ice, and the organic layer was concentrated and extracted with dichloromethane. The organic layer was dried over magnesium sulfate and concentrated to give the product (2.22 g, 96%).

Synthesis of bis (undecenoyloxymethyl) -18-crown-6-ether (I-8) Bis (hydroxymethylbenzo) -18-crown-6-ether (2.22 g, 5.28 mmol) dissolved in THF And triethylamine (6.63 mL, 31.7 mmol) was added. A THF solution of 10-undecenoyl chloride (6.42 g, 31.7 mmol) was added dropwise. The mixture was stirred at room temperature for 48 hours, and saturated aqueous sodium hydrogen carbonate solution was added. Extraction was performed with dichloromethane, and the organic layer was dried over magnesium sulfate. The concentrated residue was purified by column chromatography to obtain the target product, I-8 (1.28 g, 32%).

(Synthesis of monomer compound I-2 (triethylene glycol bisundecenoate))

  Triethylene glycol (2.00 g, 13.3 mmol) was dissolved in THF and triethylamine (5.56 mL, 39.9 mmol) was added. A THF solution of 10-undecenoyl chloride (6.74 mL, 33.3 mmol) was added dropwise. The mixture was stirred at room temperature for 48 hours, and saturated aqueous sodium hydrogen carbonate solution was added. Extraction was performed with ethyl acetate, and the organic layer was dried over magnesium sulfate. The concentrated residue was purified by column chromatography to obtain the target compound I-2 (4.00 g, 62%).

(Synthesis of monomer compound I-5 (tetraethylene glycol bisundecenoate))

  Tetraethylene glycol (3.00 g, 15.4 mmol) was dissolved in THF and triethylamine (6.44 mL, 46.2 mmol) was added. A THF solution of 10-undecenoyl chloride (7.80 mL, 38.5 mmol) was added dropwise. The mixture was stirred at room temperature for 15 hours, and saturated aqueous sodium hydrogen carbonate solution was added. Extraction was performed with ethyl acetate, and the organic layer was dried over magnesium sulfate. The concentrated residue was purified by column chromatography to obtain the target product I-5 (3.71 g, 46%).

[Production Example 9]
Sulfur (S ₈ ) (1.0 g, 3.9 mmol) and 1-undecene (II-2 compound, 0.967 g, 6.26 mmol) were placed in a reaction vessel and stirred at 175 ° C. for 60 minutes. Hexane was added to the obtained reaction product, and a soluble part and an insoluble part were filtered and separated to obtain a sulfur-containing polymer. It was Mn = 450 (hexane soluble part) when the number average molecular weight (Mn) of the said polymer was measured by GPC. As the compound of II-2, commercially available 1-undecene manufactured by Wako Pure Chemical Industries, Ltd. was used.
The physical properties of the polymers of Production Examples 2 to 9 are summarized in the following table.

Example 2 Preparation of electrode material The sulfur-containing polymer (80 mg) obtained in Production Example 6 was suspended in N-methyl-2-pyrrolidone (1.1 g), and subjected to ultrasonic vibration and heated at 100 ° C. or higher until the polymer was dissolved. did. After confirming the dissolution of the polymer, the operation of adding ketjen black (12 mg) and stirring for 10 minutes and defoaming for 5 minutes was repeated twice. To this reaction solution, a melted 8 wt% polyvinylidene fluoride N-methyl-2-pyrrolidone solution (1.1 g) was added, and the operation of stirring for 10 minutes and defoaming was repeated twice. Then, the reaction liquid was vacuum-dried at 60 degreeC for 24 hours, and the electrode material was prepared.

Example 3 Evaluation of Secondary Electrode Material Using Sulfur-Containing Polymer of the Present Invention Electrochemical by performing cyclic voltammetry (CV) measurement using the electrode material produced in Example 2 and an acetonitrile solution of magnesium bis (trifluoromethanesulfonyl) imide. The behavior was investigated. For the measurement, an electrochemical measurement system [Hokuto Denko Co., Ltd. HZ-5000 or HZ-7000] was used, and the measurement was performed with a potential scanning range of 0.2 V-2.0 V and a scanning speed of 5 mVs ⁻¹ . The results are shown in FIG. When the measurement was performed 10 times in succession, there was almost no difference in the maximum oxidation current value and the reduction current value for each measurement number, so the sulfur-containing polymer of the present invention was used as an electrode material in the positive electrode. In this case, it was found that elution of polysulfide ions (sulfur component) was suppressed. For this reason, it turned out that the sulfur-containing polymer of this invention can be utilized as a positive electrode material for secondary batteries.

Example 4 Production and evaluation of magnesium secondary battery using sulfur-containing polymer of the present invention [Production of electrode for magnesium secondary battery]
The sulfur-containing polymer (80 mg) (referred to as S-BUMB18C6) obtained in Production Example 6 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-BUMB18C6 electrode.

  The sulfur-containing polymer obtained in Production Example 5 (referred to as S-BUMB24C8) was used in the same procedure as the production of the S-BUMB18C6 electrode using the sulfur-containing polymer obtained in Production Example 6 (referred to as S-BUMB18C6). An S-BUMB24C8 electrode was produced.

[Production and evaluation of magnesium secondary battery]
Using the S-BUMB18C6 electrode or S-BUMB24C8 electrode prepared in the above (Preparation of electrode), as shown in FIG. 6, the electrode is the positive electrode, Mg (TFSA) ₂ / triethylene glycol dimethyl ether (Triglyme) is used as the electrolyte, and A magnesium secondary battery including a separator and using magnesium as a negative electrode was produced, and charge / discharge measurement was performed. The measurement result of charging / discharging of the S-BUMB18C6 electrode is shown in FIG.

The magnesium secondary battery using the S-BUMB18C6 electrode had a rate of 0.005C, a discharge capacity of 350 mAh / g, and a charge / discharge cycle of 10 cycles. The magnesium secondary battery using the S-BUMB24C8 electrode had a rate of 0.005C, a discharge capacity of 650 mAh / g, and a discharge / charge cycle of 10 cycles.
The S-BUMB18C6 electrode and the S-BUMB24C8 electrode functioned as the positive electrode of the magnesium secondary battery, and it became clear that the sulfur-containing polymer of the present invention can be used as the positive electrode material of the magnesium secondary battery.
In magnesium secondary batteries, since magnesium ions are divalent ions, the interaction with the positive electrode material is stronger than the monovalent lithium ions, and the electrode reaction (magnesium insertion / release reaction rate) is slow. there were. However, from the above results, it was found that the battery material containing the sulfur-containing polymer of the present invention is a material in which a magnesium insertion / extraction reaction easily occurs in the positive electrode and is a material suitable for the positive electrode.

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 ("High energy density rechargeable magnesium battery using earth-abundant and non- -toxic elements "Scientific Reports 4, Article number: 5622 Published 11 July 2014), its operating temperature is as high as 100 ° C. However, the operating temperature of the magnesium secondary battery using the S-BUMB18C6 electrode or the S-BUMB24C8 electrode of the present invention as the positive electrode is 25 ° C. Therefore, the secondary battery using the battery material of the present invention is excellent. It can be said.

  The sulfur-containing polymer of the present invention can be used as an electrode material of a battery including a secondary battery, and as an elastomer and a rubber material in the construction industry or the automobile industry. In addition, the sulfur-containing polymer of the present invention can be used as a positive electrode material for a magnesium secondary battery, and the magnesium secondary battery operates at room temperature. Therefore, the deterioration of the battery that occurs when operating at a high temperature can be prevented, and a battery having a long life can be obtained.

Claims (9)

Formula (I)
[Wherein R ¹ and R ³ are each independently
A linking group represented by -COO-, -OCO-, -CONH-, -NHCO-, or -O-, a substituted or unsubstituted linear or branched alkylene group having 1 to 20 carbon atoms, and a linking group; A substituted or unsubstituted linear or branched carbon number having any one or two selected from the group consisting of —COO—, —OCO—, —CONH—, —NHCO—, and —O— as a group Represents any one selected from the group consisting of 1 to 19 alkylene groups;
R ² represents a substituted or unsubstituted linear or branched alkylene group having 2 to 20 carbon atoms,
A substituted or unsubstituted linear or branched alkylene group having 2 to 20 carbon atoms, a substituted or unsubstituted aromatic group, a substituted or unsubstituted carbon number of 3 to 7 having one or more —O— in the main chain A cycloalkylene group of the formula
(Wherein, n ⁵ and n ⁶ are each independently an integer of 1 to 4, and the broken bond represents bonding to the 3rd or 4th position of the benzene ring). A diallyl compound represented by the formula (II): or any one selected from the group consisting of groups]
(Wherein R ⁴ represents a substituted or unsubstituted linear or branched alkyl group having 5 to 20 carbon atoms) and the molar ratio of the monoallyl compound represented by molecular sulfur (S ₈ ) is 1. : A sulfur-containing polymer that is a radical polymerization reaction product of 0.01 to 1: 100 and has a number average molecular weight by GPC of 300 to 10,000 . The diallyl compound represented by the formula (I) is represented by the following formula (III)
(In the formula, n ¹ and n ³ are each independently an integer of 0 to 19,
n ² is an integer of 1 to 10. The sulfur-containing polymer according to claim 1, wherein the sulfur-containing polymer is a compound represented by The diallyl compound represented by the formula (I) is represented by the following formula (V)
(Wherein n ⁴ and n ⁷ are each independently an integer of 0 to 19,
n ⁵ and n ⁶ are each independently an integer of 1 to 4,
The sulfur-containing polymer according to claim 1, wherein the bond represented by a broken line is a compound represented by the fact that it is bonded to the 3-position or 4-position of the benzene ring. Molecular sulfur (S ₈ ) After heating and melting, and the melted sulfur and formula (I)
[Wherein R ¹ And R ³ Are independent of each other
A linking group represented by -COO-, -OCO-, -CONH-, -NHCO-, or -O-, a substituted or unsubstituted linear or branched alkylene group having 1 to 20 carbon atoms, and a linking group; A substituted or unsubstituted linear or branched carbon number having any one or two selected from the group consisting of —COO—, —OCO—, —CONH—, —NHCO—, and —O— as a group Represents any one selected from the group consisting of 1 to 19 alkylene groups;
R ² Is a substituted or unsubstituted linear or branched alkylene group having 2 to 20 carbon atoms,
A substituted or unsubstituted linear or branched alkylene group having 2 to 20 carbon atoms, a substituted or unsubstituted aromatic group, a substituted or unsubstituted carbon number of 3 to 7 having one or more —O— in the main chain A cycloalkylene group of the formula
(Where n ⁵ And n ⁶ Are each independently an integer of 1 to 4, and the broken line bond represents any one selected from the group consisting of groups represented by the 3rd or 4th position of the benzene ring) A diallyl compound represented by the formula (II)

(Wherein R ⁴ Is a mixed or heated monoallyl compound represented by a substituted or unsubstituted linear or branched alkyl group having 5 to 20 carbon atoms, and is subjected to a radical polymerization reaction by heating. A method for producing a sulfur-containing polymer as described in 1. The battery material containing the sulfur-containing polymer in any one of Claims 1-3 . The battery material according to claim 5 , wherein the battery material is used for a positive electrode of a secondary battery including a primary battery or a polyvalent cation battery. The battery material according to claim 6 , wherein the negative electrode of the secondary battery is any one selected from lithium, magnesium, aluminum, and sodium. The battery material according to claim 6 , wherein the secondary battery is a magnesium secondary battery. A magnesium secondary battery comprising the battery material according to claim 8 .