WO2013099224A1

WO2013099224A1 - Network polymer and polymer gel electrolyte

Info

Publication number: WO2013099224A1
Application number: PCT/JP2012/008283
Authority: WO
Inventors: 一大山吹; 大石　勉; 鬼村　謙二郎
Original assignee: 国立大学法人山口大学
Priority date: 2011-12-27
Filing date: 2012-12-25
Publication date: 2013-07-04
Also published as: JP6253142B2; JPWO2013099224A1

Abstract

　The present invention addresses the issues of obtaining a novel network polymer having a rotaxane structure and providing a polymer gel electrolyte which can be used as the electrolyte for a secondary battery such as a lithium-ion secondary battery, and which is both highly safe and has high ionic conductivity. The network polymer according to the present invention is a network polymer having a unit (A) formed by a partial structure represented by formula (II) or (II') below being included so as to be threaded through the annular portion of a partial structure represented by formula (I) below, or, is a network polymer having said unit (A) and a unit (B) which is derived from a radically polymerizable monomer. The molar ratio ((I)/(II)) of the partial structure represented by formula (I) and the partial structure represented by formula (II) is 1/1-10/1. (Unit (A) is formed from the partial structure represented by formula (I) and the partial structure represented by formula (II), excluding cases in which unit (B) is not included.)

Description

Network polymers and polymer gel electrolytes

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

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

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

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

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

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

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

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

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

Japanese Patent No. 3475252 Japanese Patent Laying-Open No. 2005-068032 WO 2006/115255 WO2009 / 136618 JP 2009-270120 A JP 2009-051994 JP 2010-155880 A JP 2010-159336 A JP 2010-159337 A JP 2002-334690 A JP 2003-317692 A

The present invention has been made in view of such circumstances, and an object thereof is to obtain a novel network polymer having a rotaxane structure and to obtain a polymer gel electrolyte having both high safety and high ionic conductivity. .

As a result of intensive studies to solve the above problems, the present inventors have succeeded in building a novel network polymer having a rotaxane structure using a crown ether, and the polymer gel electrolyte obtained from the network polymer has high safety. And the present invention has been completed.

That is, the present invention
(1) The following 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 portion of the partial structure represented by the chain, 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.
Following 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 chain, a hydrocarbon group having 1 to 15 carbon atoms, Z ^-. represents a counter anion), or the following 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 network polymer having a unit (A), or a network polymer having a unit (B) derived from the unit (A) and a radical polymerizable monomer,
A network polymer in which the molar ratio ((I) / (II)) between the partial structure represented by the formula (I) and the partial structure represented by the formula (II) is 1/1 to 10/1 (however, The unit (A) consists of a partial structure represented by the formula (I) and a partial structure represented by the formula (II), excluding a case where the unit (A) does not have the unit (B)),
(2) The molar ratio ((A) / (B)) between the unit (A) and the unit (B) derived from the radical polymerizable monomer is from 1/1 to 1/100 (1) ) Network polymers,
(3) The network polymer according to (1), wherein the partial structure represented by the formula (I) is a structure represented by the following formula (III):

(In the formula, m is an integer of 1 to 13, and the bond in the dotted line part is bonded to either the 3-position or 4-position of the benzene ring. N2 is the same as defined in formula (I). ),
(4) The network polymer according to (1), wherein the partial structure represented by the formula (II) is a structure represented by the following formula (IV):

(Wherein y represents an integer of 1 to 12, Z ⁻ represents a counter anion), and
(5) The radical polymerizable monomer is one or more compounds selected from the group consisting of methyl methacrylate, n-butyl methacrylate, 2-hydroxyethyl methacrylate, polyethylene glycol methacrylate, styrene and acrylonitrile. It is related with the network polymer as described in (1).

The present invention also provides:
(6) Formula (V)

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 The chain represents a hydrocarbon group having 1 to 15 carbon atoms, and X ₁ and X ₂ are the same or different and represent a group that acts as a bonding site during the polymerization reaction, and n1 represents an integer of 3 or 4.) A cyclic compound represented by:
Following formula (VI)

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 The chain represents a hydrocarbon group having 1 to 15 carbon atoms, and X ₃ and X ₄ are the same or different and each represents a group that acts as a binding site during the polymerization reaction, and Z ⁻ represents a counter anion). A structure in which the partial structure represented by the formula (II) is included in a skewered manner in the cyclic part of the partial structure represented by the formula (I) A method for producing a network polymer according to (1), wherein after the formation of the compound having A), the compound having the structure (A) is polymerized,
(7) The following formula (VII)

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 The chain represents a hydrocarbon group having 1 to 15 carbon atoms, and X ₁ and X ₂ are the same or different and each represents a group that acts as a binding site during a polymerization reaction or a group that does not act as a binding site during a polymerization reaction, provided that When n2 is 1, it is limited to the case where X ₁ and X ₂ are groups acting as a binding site during the polymerization reaction.
n1 represents an integer of 3 or 4. n2 represents an integer of 1 to 30. And a cyclic compound represented by
Following formula (VI)

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 The chain represents a hydrocarbon group having 1 to 15 carbon atoms, and X ₃ and X ₄ are the same or different and each represents a group that acts as a binding site during the polymerization reaction, and Z ⁻ represents a counter anion). Reaction with a linear compound
After generating the compound having the structure (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), The method for producing a network polymer according to (1), wherein the compound having the structure (A) and a radically polymerizable monomer are radically polymerized, and
(8) After polymerization, the obtained network polymer is further reacted with an electrophile,
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 A partial structure represented by the formula (II ′): a chain of a hydrocarbon group having 1 to 15 carbon atoms, and Z ⁻ represents a counter anion.

(Wherein R ₃ and R ₄ are the same as defined in formula (II), and R ₅ represents a residue derived from an electrophile). The present invention relates to a method for producing a network polymer according to 6) or (7).

Furthermore, the present invention provides:
(9) A polymer gel electrolyte comprising the network polymer according to any one of (1) to (5) in an electrolytic solution,
(10) The polymer gel electrolyte according to (9), wherein the electrolytic solution is a propylene carbonate solution or an ethylene carbonate solution of lithium hexafluorophosphate or lithium tetrafluoroborate, and
(11) A secondary battery using the polymer gel electrolyte according to (9).

According to the present invention, by containing a rotaxane structure having a crosslinking point consisting of an inclusion structure formed from a specific linear compound and a cyclic molecule, the temperature and solvent are compared with those of conventional physical gels and chemical gels. A network polymer gel with high stability and mechanical strength is provided. In addition, when a radically polymerizable monomer is included as the third polymerization component, a network polymer gel that is flexible, has high mobility, and has excellent film formability compared to a network polymer composed only of a linear compound having a rotaxane structure and a cyclic molecule. Provided. The novel network polymer having a rotaxane structure of the present invention is a polymer gel electrolyte having both high safety and high ionic conductivity, and the polymer gel electrolyte is used as an electrolyte for a non-aqueous electrolyte secondary battery such as a lithium ion secondary battery. Is possible.

When the network polymer of the present invention is used for a polymer gel electrolyte, higher ion transport efficiency can be obtained as compared with conventional network polymers. When a network polymer in which -N ⁺ H ₂ -groups are neutralized is used, the conductivity is improved and the content of the electrolyte solution is further increased as compared with the network polymer having -N ⁺ H ₂ -groups. Can be reduced.

It is a figure which shows the NMR spectrum of the network polymer after the pseudo rotaxane structure which consists of cyclic compound (i) and linear compound (iv) in the synthesis example 1, and a polymerization reaction. It is a figure which shows IR spectrum of the network polymer after the polymerization reaction in the synthesis example 1. (A) ¹ H-NMR spectrum of cyclic compound (iii), linear compound (iv), methyl methacrylate mixed solution before polymerization, and (b) ¹ H-NMR spectrum of network polymer gel after polymerization It is. It is a figure which shows the IR spectrum of the neutralized network polymer in the synthesis example 38. It is a figure which shows the IR spectrum of the network polymer gel (Synthesis example 15) before (a) acetylation, and the network polymer gel (Synthesis example 39) after (b) acetylation.

1 Network Polymer of the Present Invention The network polymer of the present invention includes a network polymer having a —N ⁺ H ₂ — group and a network polymer in which a —N ⁺ H ₂ — group is neutralized with an electrophile.

[Network polymer having -N ⁺ H ₂ -group (network polymer A)]
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 A-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 A-2”). ).

In the formula, 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 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 which 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, and Z ⁻ represents a counter anion.
However, the present invention does not include the network polymer A-1 consisting only of the unit (A).

Represented by 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”, “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: ethylidene, propylidene, isopropylidene, sec-butylidene, tert-butylidene, n-pentylidene, 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 limited to these, in view of steric hindrance and the like, a carbon number of 1 to 11 is more preferable.

In the partial structure represented by the formula (II), the counter ion 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). It is possible to construct a rotaxane structure or pseudo-rotaxane structure in which the partial structure is included in a skewered manner, and in the unit derived from the partial structure represented by the formula (II) in the rotaxane structure or pseudo-rotaxane structure— Any monovalent anion capable of converting an N ⁺ H ₂ — group into an —NR ₅ — group (R ₅ represents a residue derived from an electrophile) may be used.
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 ⁻ 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.
Rf contained in the anion represented by N (RfSO ₃ ) ₂ ⁻ , C (RfSO ₃ ) ₃ ⁻ , RfSO ₃ ^— or RfCO ₂ ^— 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 radically polymerizable monomer” is a structure contained in the network polymer A-2, and the radically polymerizable monomer is not particularly limited as long as it is a compound having radical polymerizability. 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 such as a group represented by

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 acrylate, (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.
Of these, methyl methacrylate, n-butyl methacrylate, 2-hydroxyethyl methacrylate, polyethylene glycol methacrylate, styrene and acrylonitrile are preferred.

In the network polymer A, 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 forming a network, another pseudo-rotaxane unit or another pseudo-rotaxane unit bonded via a radical polymerizable monomer serves as a stopper, so that the ring and the axis are not separated.

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

“Network polymer A-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 A 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 and ethyl acetate.

As the compound represented by the formula (I) and the compound represented by the formula (II), commercially available ones can be used, and the compound can be produced by a conventionally known method (Non-patent Document 1).

The partial structure represented by the formula (I) is preferably a partial structure represented by the following 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 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 the formula, y is an integer of 1 to 12, Z ⁻ is a counter anion, and examples thereof are the same as those in formula (II).

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

In the network polymer B, 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 which 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 Examples of the hydrocarbon group having 1 to 15 carbon atoms are the same as those in the 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 crown ether ring, R ₅ preferably has about 1 to 11 carbon atoms.

Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, i-propyl group, cyclopropyl group, n-butyl group, sec-butyl group, i-butyl group, tert-butyl group, 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 a benzylcarbonyl group, a cinnamoyl group, a hydrocinnamoyl group, and a naphthalenylacetyl group.

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.

2 Method for producing network polymer of the present invention [Production of network polymer A]
(First stage)
The first step for producing the network polymer A 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 the formula, 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 And X ₁ and X ₂ are the same or different and each represents a group that acts as a bonding site during the polymerization reaction. n1 represents an integer of 3 or 4.

In which 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 And X ₃ and X ₄ are the same or different and each represents a group that acts as a bonding site during the polymerization reaction. Z ⁻ represents a counter anion.

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

In the formula, 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 And X ₁ and X ₂ are the same or different and represent a group that acts as a binding site during a polymerization reaction or a group that does not act as a binding site during a polymerization reaction. n1 represents an integer of 3 or 4, and n2 represents an integer of 2 to 30.

Represented by 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”, “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: ethylidene, propylidene, isopropylidene, sec-butylidene, tert-butylidene, n-pentylidene, 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. However, the number of carbon atoms is not limited to these, and a carbon number of 1 to 11 is more preferable from the viewpoint of steric hindrance and the like.

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 A-2, and X ₁ and X ₂ are represented by the formula (V) when n2 = 1. After the resulting compound 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 bonding 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 the compound represented by the formula (VI), the counter ion represented by Z ⁻ is not particularly limited, but the moiety represented by the formula (VI) is added to the cyclic part of the partial structure represented by the formula (V). -N in a unit derived from the partial structure represented by the formula (VI) in the rotaxane structure or pseudo-rotaxane structure, in which a rotaxane structure or pseudo-rotaxane structure in which the structure is included in a skewered manner can be constructed Any monovalent anion capable of converting a ⁺ H ₂ — group into a —NR ₅ — group (R ₅ represents a residue derived from an electrophile) may be used.
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 ⁻ 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.
Rf contained in the anion represented by N (RfSO ₃ ) ₂ ⁻ , C (RfSO ₃ ) ₃ ⁻ , RfSO ₃ ^— or RfCO ₂ ^— represents a fluoroalkyl group having 1 to 12 carbon atoms, trifluoromethyl, Examples include fluorinated alkyl groups such as pentafluoroethyl, heptafluoropropyl and nonafluorobutyl.

When the compound represented by the formula (V) and the linear compound represented by the formula (VI) are mixed, the N ⁺ in the compound represented by the formula (VI) is added to the crown ether ring in the formula (V). A structure (A) in which an H ₂ group is included, that is, a pseudo-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 molar ratio. is there. The formation of the pseudorotaxane 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 in the polymerization reaction of the cyclic compound represented by the formula (V) or the formula (VII) have a carbon-carbon double bond, 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 to this, it is conceivable to saturate the carbon-carbon double bonds of X ₁ and X ₂ by a catalytic hydrogenation reaction after completion of the polymerization reaction, but the conversion method is not limited to this.

When the compound represented by the formula (V) or the formula (VII) and the compound represented by the formula (VI) are mixed, the compound represented by the formula (V) or the formula (VII) has a formula (V) A structure (A) in which an N ⁺ H ₂ group in the compound represented by VI) is included, that is, a pseudo-rotaxane complex is formed. Here, the mixing ratio of the compound represented by the formula (V) or the formula (VII) and the compound represented by the formula (II) is 1 to 10: 1, preferably 1 to 3: 1 in terms of molar ratio. Preferably it is 1: 1. The formation of the pseudorotaxane complex can be confirmed by ¹ H-NMR measurement.

The structure (A) is formed when a compound represented by the formula (V) or the formula (VII) and a compound represented by the formula (VI) are mixed in a solvent and their ¹ H-NMR is measured. The chemical shift of protons near the ammonium salt of the compound represented by the formula (VI) can be confirmed by shifting to a low magnetic field.

(Second stage)
In the second stage of the production of the network polymer A of the present invention, the structure (A) formed in the first stage is polymerized (production of the network polymer A-1), or the structure (A) and the radical polymerizable monomer are polymerized. (Manufacture of network polymer A-2).
The pseudo-rotaxane 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. . The structure of the network polymer after polymerization can be controlled by selecting the reactivity of the polymerizable functional groups X ₁ to X ₄ or the polymerization method.

In the production of the network polymer A-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). However, 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 A-2, the polymerization reaction between the structure (A) and the radically polymerizable monomer is a partial structure represented by the formula (I) and the formula (II) in the network polymer produced by the polymerization. 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 pseudorotaxane 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. The reaction conditions are not particularly limited, but the reaction is usually carried out in an organic solvent such as chloroform and toluene at room temperature to 100 ° C. for 1 to 24 hours.

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.

The polymerization initiator used may be a conventionally known polymerization initiator such as 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-imidazolin-2-yl) propane] Azo initiators such as dihydrochloride; persulfate initiators such as potassium persulfate and ammonium persulfate; peroxide initiators such as benzoyl peroxide, t-butyl hydroperoxide and hydrogen peroxide It is done.
In particular, as photopolymerization initiators, 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. These polymerization initiators may be used alone or in combination of two or more.

[Manufacture of network polymer B]
The network polymer A 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 B 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 crown ether ring, 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, chloride Opentyl, 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 Neniru, 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.

Using the linear or branched alkyl halide, the linear or branched alkenyl halide, or the arylalkyl halide, the —NR ⁺ H ₂ — group of the partial structure represented by the formula (II) _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 thereof 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 does not have 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, Phthalene chloride, naphthalene bromide, furan carboxylic acid chloride, furan carboxylic acid bromide, thiophene carboxylic acid chloride, thiophene carboxylic 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 the 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.

Examples of the anhydrous carbonic acid diester as the electrophile include 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.

Using the acid halide, acid anhydride, carbonic acid halide, anhydrous carbonic acid diester, alkylsulfonyl halide, arylsulfonyl halide or the like, the —N ⁺ H ₂ — group of the partial structure represented by the formula (II) is represented by the formula (II ′ The method for converting the partial structure represented by (II) to the —NR ₅ — group is not particularly limited as long as it can be converted. For example, a base and the above acid halide, acid anhydride, carbonate halide, carbonate anhydride In the presence of a diester, an alkylsulfonyl halide, an arylsulfonyl halide, or the like, 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 the —N ⁺ H ₂ — group to the —NR ₅ — group may be 10% or more, preferably 30% or more, more preferably 50% or more.

The network polymer A before reacting with the electrophile attracts the crown ether ring in the partial structure represented by the formula (I) and the —N ⁺ H ₂ — group in the partial structure represented by the formula (II). Fit. 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 A. It can be confirmed by IR measurement that at least part of the —N ⁺ H ₂ — group is converted to the —NR ₅ — group.

The network polymer A and the network polymer B of the present invention 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, phosphoric acid 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.

3 Polymer Gel Electrolyte The polymer gel electrolyte of the present invention is obtained by mixing the above-described network polymer A and / or B with an electrolyte solution.
Since the network polymer A and / or B has a gelling ability with respect to various solvents, the polymer polymer electrolyte is formed by containing the network polymer A and / or B and an electrolyte solution.

As the electrolyte, a conventionally known inorganic ion salt used for a non-aqueous electrolyte solution can be used. For example, lithium chloride (LiCl), lithium perchlorate (LiClO ₄ ), lithium hexafluoroarsenate (LiAsF _6). ), Lithium hexafluorophosphate (LiPF ₆ ), lithium tetrafluoroborate (LiBF ₄ ), lithium tetraphenylborate (LiB (C ₆ H ₅ ) ₄ ), lithium methanesulfonate (LiCH ₃ SO ₃ ), Lithium trifluoromethanesulfonate (LiCF ₃ SO ₃ ), bis (pentafluoroethanesulfonyl) imide lithium (Li (C ₂ F ₅ SO ₂ ) ₂ N), bis (trifluoromethanesulfonyl) imide lithium (Li (CF ₃ SO ₂₎ ) ₂ N), tris (trifluoromethanesulfonyl) Mechirurichi Beam _{_{_{(LiC (CF 3 SO 2)}}} 3), it is possible to use lithium bromide (LiBr), may be used by mixing two or more of these.

As the solvent, a conventionally known solvent used for a non-aqueous electrolyte solution can be used. For example, 4-fluoro-1,3-dioxolan-2-one, ethylene carbonate, propylene carbonate, vinylene carbonate, dimethyl carbonate, ethyl Methyl carbonate, γ-butyrolactone, γ-valerolactone, 1,2-dimethoxyethane, 1,2-diethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, 4-methyl-1,3-dioxolane, Diethyl ether, methyl acetate, methyl propionate, ethyl propionate, propionate acetonitrile, propionitrile, anisole, acetate, butyrate, glutaronitrile, adiponitrile, methoxyacetonitrile, 3 -Methoxypropionitrile, N, N-dimethylformamide, N-methylpyrrolidinone, N-methyloxazolidinone, nitromethane, nitroethane, sulfolane, methylsulfolane, dimethyl sulfoxide, trimethyl phosphate, triethyl phosphate, ethylene sulfide, bistrifluoromethylsulfonyl Imidotrimethylhexylammonium and the like can be used, and two or more of these can also be mixed and used.

Among electrolyte solutions in which the inorganic ion salt is dissolved in the solvent, a solvent containing at least one selected from the group consisting of 1,2-dimethoxyethane, diethyl carbonate, and methyl ethyl carbonate, and ethylene carbonate or propylene carbonate In addition, an electrolyte solution in which at least one inorganic ion salt selected from the group consisting of LiClO ₄ , LiBF ₄ , LiPF ₆ and LiCF ₃ SO ₃ is dissolved is preferable. The concentration of the inorganic ion salt in the electrolytic solution is preferably about 0.2 to 3.0 mol / L, for example.

The polymer gel electrolyte of the present invention can be obtained by gelling an electrolyte solution with the network polymer A and / or B. Specifically, a production method in which a predetermined amount of network polymer A and / or B is dissolved in a predetermined amount of electrolyte solution by heating and then cooled is exemplified. Usually, it is preferable to dissolve completely by heating.
When the network polymer of the present invention is used, the content of the electrolyte solution can be reduced, but the polymer gel electrolyte using the network polymer B is more electrolyte solution than the polymer gel electrolyte using the network polymer polymer A. The content of can be further reduced.
That is, the amount of the electrolyte solution used with respect to the network polymer A is 10 to 300 parts by mass, preferably 100 to 200 parts by mass with respect to 100 parts by mass of the network polymer A.
On the other hand, the amount of the electrolyte solution used for the network polymer B is 10 to 100 parts by mass, preferably 10 to 50 parts by mass with respect to 100 parts by mass of the network polymer B.

4 Nonaqueous electrolyte secondary battery The polymer gel electrolyte can be used as a nonaqueous electrolyte secondary battery such as a lithium ion secondary battery.

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

For example, the positive electrode is not particularly limited as long as it absorbs positive ions or discharges negative ions during discharge, and is not limited to metal oxides such as LiMnO ₂ , LiMn ₂ O ₄ , LiCoO ₂ , LiNiO ₂ , or polyacetylene. Conventionally known materials for secondary batteries such as conductive polymers such as polyaniline, polypyrrole, polythiophene and polyparaphenylene, derivatives thereof, and disulfide compounds can be used.

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

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

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

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

Further, the shape of the nonaqueous electrolyte secondary battery of the present invention is not particularly limited. 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 to these examples.

1 Synthesis of cyclic compounds
(1) The cyclic compound (i) 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) were 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 monotosylate (29.4 g, 0.097 mol) and potassium carbonate (15.3 g, 0.10 mol) in acetone (240 mL). Dissolved 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) were 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] 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 the mixture was 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 a solution of bis (ethoxycarbonylbenzo) -24-crown-8-ether (2.93 g, 4.94 mmol). Reflux for 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%).

Bis (hydroxymethylbenzo) -24-crown-8-ether (2.46 g, 4.84 mmol) was dissolved in THF, and 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 cyclic compound (i) (2.78 g, 68%).

(2) The cyclic compound (ii) was synthesized by the following procedure.

[Synthesis of bis (formylbenzo) -24-crown-8-ether]
2 mL of trifluoroacetic acid was added to 0.50 g (1.14 mmol) of dibenzo-24-crown-8-ether (DB24C8: manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.799 g (5.70 mmol) of hexamethylenetetramine, and an oil bath at 60 ° C. Heated in for 24 hours. Then 5 mL of distilled water was added, extracted with dichloromethane (100 mL × 3), dried over anhydrous magnesium sulfate and concentrated. Purification by column chromatography (silica gel, dichloromethane: methanol = 10: 1). Yellowish white crystals were obtained in a yield of 82% (0.473 g).

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

[Synthesis of bis (methacryloyloxymethylbenzo) -24-crown-8-ether (cyclic compound (ii))]
Bis (hydroxymethylbenzo) -24-crown-8-ether (1.00 g, 1.97 mmol) was dissolved in THF (25 mL). Further, 2.7 mL (19.7 mmol) of triethylamine was added. A THF solution (5 mL) of 1.03 mL (9.85 mmol) of methacrylic acid chloride was slowly added dropwise to the solution at 0 ° C. using a dropping funnel and stirred. After stirring at 0 ° C. for 10 minutes, the mixture was returned to room temperature and stirred for 24 hours. 5 mL of an aqueous sodium hydrogen carbonate solution was added, and only THF was removed by concentration. Thereafter, the mixture was extracted with ethyl acetate, dried over anhydrous magnesium sulfate and concentrated. Thereafter, the residue was purified by column chromatography (silica gel, ethyl acetate: hexane = 1: 1). White crystals were obtained with a yield of 71% (0.81 g).
¹ H-NMR (CDCl ₃ ) (δ, ppm from TMS): 6.98-6.80 (m, 6H, Ph), 6.15-6.10 (m, 1H, methacryl group), 5.60 −5.54 (m, 1H, methacryl group), 5.08 (s, 2H, —CH ₂ —), 4.18-4.12 (m, 8H, —CH ₂ —CH ₂ —O—), 3.96-3.89 (m, 8H, —CH ₂ —CH ₂ —O—), 3.86-3.80 (m, 8H, —CH ₂ —CH ₂ —O—), 2.00— 1.86 (m, 3H, —CH ₂ —CH ₂ —O—).

(3) Synthesis of cyclic compound (iii) The cyclic compound (iii) was synthesized by the following procedure.

[Synthesis of bis (undec-10-enoyloxymethylbenzo) -24-crown-8-ether]
To a THF solution of 3 g (5.90 mmol) of bis (hydroxymethylbenzo) -24-crown-8-ether was added 4.11 mL (29.5 mmol) of triethylamine, and 5.98 g (29.29 g) of 10-undecenoyl chloride. 5 mmol) in THF was slowly added dropwise. The mixed solution was stirred at room temperature for 36 hours and quenched by adding saturated aqueous sodium carbonate solution. Thereafter, the solution was extracted with dichloromethane, and the organic layer was dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure, and the product was purified by reprecipitation in a dichloromethane / hexane system after washing with hexane. A white solid was obtained in a yield of 75% (3.74 g).
¹ H-NMR (CDCl ₃ ) (δ, ppm from TMS): 6.92-6.79 (m, 6H, Ph), 5.89-5.73 (m, 1H, CH ₂ ═CH—), 5.05-4.88 (m, 8H, CH ₂ ═CH—, Ph—CH ₂ —O—CO—), 4.18-3.79 (m, 24H, —CH ₂ CH ₂ O—), 2.36-2.26 (m, 4H, —CH ₂ —COO—), 2.08-1.96 (m, 4H, CH ₂ ═CH—CH ₂ —), 1.70-1.55 ( m, 4H, —CH ₂ CH ₂ —COO—), 1.43-1.20 (m, 20H, CH ₂ ═CH—CH ₂ — (CH ₂ ) ₅ —).

[Synthesis of polybis (undec-10-enoyloxymethylbenzo) -24-crown-8-ether (cyclic compound (iii))]
Bis (undec-10-enoyloxymethylbenzo) -24-crown-8-ether 0.5 g (0.62 mmol) and first generation Grubbs catalyst 25 mg (0.031 mmol) in dichloromethane solution (3 mL) for 24 hours Refluxed. The reaction was stopped by adding ethyl vinyl ether and concentrated under reduced pressure. The concentrate was purified by reprecipitation with a dichloromethane / methanol system. A gray solid was obtained in 84% yield (0.42 g). The number average molecular weight (Mn) in terms of polystyrene measured by GPC was 5600.

2 Synthesis of linear compound (1) The linear compound (iv) was synthesized by the following procedure.

(Synthesis of tert-butyl N, N-bis (2-hydroxyethyl) carbamate)
Diethanolamine (15.0 g, 0.014 mol) and 4- (dimethylamino) pyridine (0.175 g, 1.43 mmol) were dissolved in chloroform (250 mL), and di-tert-butyl dicarbonate (31.2 g, 0 .014 mol) was added and stirred at room temperature for 3 hours. The solvent was distilled off, and the residue was purified by column chromatography to obtain t-butyl N, N-bis (2-hydroxyethyl) carbamate (28.1 g, 96%).

(Synthesis of tert-butyl N, N-bis (undecenoyloxyethyl) carbamate)
A solution of tert-butyl N, N-bis (2-hydroxyethyl) carbamate (14.9 g, 0.0723 mol) and triethylamine (50 mL, 0.362 mol) in tetrahydrofuran (hereinafter abbreviated as THF. 50 mL) was brought to 0 ° C. Cooled down. A solution of 10-undecenoyl chloride (44.0 g, 0.217 mol) in THF (50 mL) was added, and the mixture was stirred at 0 ° C. for 10 minutes and at room temperature for 86 hours. Saturated aqueous sodium hydrogen carbonate solution was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by column chromatography to obtain tert-butyl N, N-bis (2-hydroxyethyl) carbamate (37.1 g, 95%).

(Synthesis of N, N-bis (undecenoyloxyethyl) ammonium hexafluorophosphate (iv))
To a solution of tert-butyl N, N-bis (2-hydroxyethyl) carbamate (3.00 g, 5.58 mmol) in chloroform (3 mL) was added trifluoroacetic acid (3 mL), and the mixture was stirred at room temperature for 4 hours. Distilled under reduced pressure, the residue was diluted in dichloromethane and washed with saturated aqueous ammonium hexafluorophosphate. The organic layer was dried over magnesium sulfate and the solvent was distilled off to obtain N, N-bis (undecenoyloxyethyl) ammonium hexafluorophosphate (iv) (2.25 g, 69%).

(2) The linear compound (v) was synthesized by the following procedure.

[Synthesis of tert-butyl N, N-bis (hydroxyethyl) carbamate]
To 10 g (95.1 mmol) of diethanolamine was dissolved 100 mL of chloroform, and 0.12 g (0.951 mmol) of N, N-dimethylaminopyridine (DMAP) was added to the solution. Thereafter, while cooling the solution at 0 ° C., 10.4 g (47.5 mmol) of di-tert-butyl dicarbonate was added and stirred. After 10 minutes, the mixture was returned to room temperature and stirred for 5 hours. The reaction solution was concentrated and purified by column chromatography (silica gel, ethyl acetate: methanol = 10: 1). A colorless liquid was obtained with a yield of 96% (8.6 g).

[Synthesis of tert-butyl N, N-bis (methacryloyloxyethyl) carbamate]
To a THF solution (10 mL) of 1 g (5.29 mmol) of tert-butyl N, N-bis (hydroxyethyl) carbamate, 1.61 g (15.9 mmol) of triethylamine was added. A THF solution (5 mL) of 1.66 mL (15.9 mmol) of methacrylic acid chloride was slowly dropped into the solution at 0 ° C. using a dropping funnel and stirred. After stirring at 0 ° C. for 10 minutes, the mixture was returned to room temperature and stirred for 24 hours. 5 mL of a saturated aqueous sodium hydrogen carbonate solution was added, and only THF was removed by concentration. The mixture was extracted with ethyl acetate, and the organic layer was dried over anhydrous magnesium sulfate and concentrated. Thereafter, purification was performed by column chromatography (silica gel, ethyl acetate: hexane = 1: 9). A colorless liquid was obtained with a yield of 76% (1.36 g).

[Synthesis of bis (methacryloyloxyethyl) amine hexafluorophosphonate (linear compound (v))]
Trifluoroacetic acid (1 mL) was added to a chloroform solution (1 mL) of 0.33 g (1 mmol) of tert-butyl N, N-bis (methacryloyloxyethyl) carbamate and allowed to react at room temperature for 5 hours. After the reaction, trifluoroacetic acid and chloroform were removed by distillation under reduced pressure. Thereafter, it was diluted with dichloromethane (10 mL) and washed with an aqueous ammonium hexafluorophosphate solution. The extract was dried over anhydrous magnesium sulfate and concentrated. A white solid was obtained in 41% yield (0.16 g).
¹ H-NMR (CDCl ₃ ) (δ, ppm from TMS): 6.09-6.15 (1H, m, —CH ₂ ═CH), 5.89-5.71 (1H, m, —CH ₂ = CH), 4.28-4.15 (4H, s, -COOCH _2- ), 3.84-3.71 (4H, s, -CH ₂ -N-), 1.97-1.89 ( 6H, m, CH ₃ -C-).

3 Synthesis of network polymer A
[Synthesis Example 1]
[Synthesis of network polymer using olefin metathesis reaction]
A Grubbs catalyst (benzylidenebis (tricyclohexylphosphine) dichlororuthenium) was added to a dichloromethane solution of the cyclic compound (i) and the linear compound (iv), and the mixture was stirred at 40 ° C. for 24 hours. Ethyl vinyl ether was added, and the product was washed several times with dichloromethane and DMF to obtain a network polymer having a structure in which the rotaxane unit composed of the cyclic compound (i) and the linear compound (iv) was polymerized.
The NMR spectra before and after the reaction are shown in FIG. In FIG. 1, the signals c and d are derived from the hydrogen atom of the terminal olefin of the linear compound (iv), respectively. In the spectrum after the reaction, the signal intensities of c and d decreased, and a signal e derived from a double bond produced by the olefin metathesis reaction was newly observed.

[Synthesis Example 2-7]
[Synthesis of network polymer using radical polymerization reaction 1: Reaction by heat]
In the composition shown in Table 1, a cyclic compound, a linear compound, azobisisobutyronitrile (AIBN) and a third component are mixed and reacted in chloroform to obtain a cyclic compound (i) and a linear compound ( A network polymer having a structure in which the rotaxane unit consisting of iv) or (v) was polymerized was obtained.

Compound a: methyl methacrylate compound b: butyl methacrylate compound c: 2-hydroxyethyl methacrylate compound d: methoxypolyethylene glycol methacrylate

[Synthesis Example 8-13]
[Synthesis of network polymer using radical polymerization reaction 2: Reaction by ultraviolet light]
In the composition shown in Table 2, a linear compound, a macrocyclic compound, benzophenone and a third component are mixed, irradiated with ultraviolet light under the following conditions, and the cyclic compound (i) and the linear compound (iv) or A network polymer having a structure in which the rotaxane unit consisting of (v) was polymerized was obtained.
Irradiation device: Ishii Shoten Co., Ltd. photochemical UV generator Irradiation wavelength: 255 nm or later. Main wavelength is 300nm ~ 450nm (with bright line at 480nm ~ 580nm)
Irradiation temperature: Room temperature Irradiation time: 24 hours

[Synthesis Example 14]
42 mg (0.13 mmol) of the cyclic compound (ii) and 38 mg (0.13 mmol) of the linear compound (v) were dissolved in 0.1 mL of chloroform. Further, 65 mg (0.65 mmol) of methyl methacrylate was added and applied to a slide glass. After the solvent was dried, the reaction was carried out by UV irradiation for 24 hours. The UV lamp was 200 W using a high-pressure UV-HT type (Ishii Shoten Co., Ltd.), an ultraviolet generation reaction apparatus for photochemistry. After the reaction, it was washed several times with dimethylformamide and chloroform. Thereafter, a yellow network polymer gel was obtained by drying.

[Synthesis Example 15]
20 mg (0.0246 mmol) of the cyclic compound (iii) and 14 mg (0.0246 mmol) of the linear compound (iv) were dissolved in 0.2 mL of chloroform. Further, 3.14 mg (0.0172 mmol) of benzophenone and 12.3 mg (0.123 mmol) of methyl methacrylate were added and cast on a slide glass. The solvent was dried and reacted for 24 hours by UV irradiation. The UV lamp was 200 W using a high-pressure UV-HT type (Ishii Shoten Co., Ltd.), an ultraviolet generation reaction apparatus for photochemistry. After the reaction, it was washed several times with DMF and methanol. Thereafter, a purple network polymer gel was obtained by drying.

[Reference example]
20 mg (0.0246 mmol) of the cyclic compound (iii) and 14 mg (0.0246 mmol) of the linear compound (iv) were dissolved in 0.2 mL of chloroform. Further, benzophenone (BP) and methyl methacrylate (MMA) in the amounts shown in Table 3 were added, and the mixture was cast on a slide glass. The solvent was dried and reacted for 2 hours by UV irradiation. The UV lamp was 200 W using a high-pressure UV-HT type (Ishii Shoten Co., Ltd.), an ultraviolet generation reaction apparatus for photochemistry. After the reaction, it was washed several times with DMF and methanol. Thereafter, it was dried to obtain a network polymer gel. It was found that the state of the synthesized network polymer gel changes depending on the amount of methacrylate.

In order to confirm the network structure in the gel, the gelation process was investigated by ¹ H-NMR spectrum. FIG. 3 shows ¹ H-NMR spectra before and after the polymerization reaction. Gelation was performed by NMR containing 80 mg (0.0984 mmol) of the cyclic compound (iii), 56 mg (0.0984 mmol) of the linear compound (iv), 5 equivalents of methyl methacrylate and 10 mol% of azobisisobutyronitrile in a deuterated chloroform solvent. This was done by heating the sample tube. From the spectrum of (a) before the polymerization reaction, it was confirmed that a pseudorotaxane was formed from the integrated value of the shifted peak of the methylene proton near the ammonium salt. In (b) after the polymerization reaction, since the peak derived from the double bond of MMA disappeared, the progress of the reaction of MMA was confirmed. Moreover, it was confirmed from the integrated value of the shifted peak of methylene protons near the ammonium salt that pseudo rotaxane was formed, and these results suggested that the network polymer had a rotaxane structure at the crosslinking point.

[Synthesis Examples 16 to 20]
20 mg (0.0246 mmol) of the cyclic compound (iii) and 14 mg (0.0246 mmol) of the linear compound (iv) were dissolved in 0.2 mL of chloroform. Further, 3.14 mg (0.0172 mmol) of benzophenone and the radical polymerizable monomer (monomer) shown in Table 2; butyl methacrylate (BMA), 2-hydroxyethyl methacrylate (HEMA), polyethylene glycol methyl ether monomethacrylate (PEGMA) Any one of styrene (St) and acrylonitrile (An) was added and cast onto a glass slide. The solvent was dried and reacted for 24 hours by UV irradiation. After the reaction, it was washed several times with DMF and methanol. Thereafter, the polymer polymer gel shown in Table 4 was obtained by drying.

[Synthesis Examples 21 to 37]
20 mg (0.0246 mmol) of the cyclic compound (iii) and 4.7 mg (0.0082 mmol) of the linear compound (iv) were dissolved in 0.2 mL of chloroform. Further, benzophenone and the radical polymerizable monomer shown in Table 5 were added, and the mixture was cast on a slide glass. The solvent was dried and reacted by UV irradiation. The UV lamp was 200 W using a high-pressure UV-HT type (Ishii Shoten Co., Ltd.), an ultraviolet generation reaction apparatus for photochemistry. After the reaction, it was washed several times with DMF and methanol. Thereafter, it was dried to obtain a network polymer gel.

[Measurement of swelling degree of network polymer gel]
Table 6 shows the results of measurement of swelling degree using methanol, dichloromethane (DCM) and dimethyl sulfoxide (DMSO) for the network polymer gels produced in Synthesis Examples 15, 19, 20, 21, 34, and 37. Show.

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

The network polymer gel swelled well when dichloromethane was used, and hardly swelled when methanol was used. Moreover, the difference of the swelling degree by the ratio of the linear compound in a network polymer gel, a cyclic compound, and a radical polysynthetic monomer was not seen so much.

4 Synthesis of Network Polymer B [Synthesis Example 38]
The network polymer (8.9 mg) obtained in Synthesis Example 1 was added to acetonitrile, and triethylamine (0.091 mL, 0.0651 mmol) and acetic anhydride (0.062 mL, 0.651 mmol) were further added. The solution was heated and stirred at 40 ° C. for 24 hours. After completion of the reaction, the network polymer was washed with methanol and dried to obtain a neutralized network polymer (yield: 7.6 mg).
FIG. 2 shows the IR spectrum of the network polymer obtained before the reaction with the electrophile, that is, in Synthesis Example 1, and FIG. 4 shows the IR spectrum after the reaction. A new peak (1670-1640 cm ⁻¹ ) derived from a tertiary amide bond was observed due to the reaction with the electrophile.

[Synthesis Example 39]
Acetonitrile, triethylamine, and acetic anhydride were added to the network polymer gel produced in Synthesis Example 15 to acetylate the nitrogen atom of the —N ⁺ H ₂ — group in the repeating unit derived from formula (II) in the network polymer gel. It was. The reaction was carried out at 50 ° C. for 24 hours, and washed with methanol after the reaction. FIG. 5 shows FT-IR spectra before and after acetylation. In (b) after acetylation, a new C═O stretching vibration derived from an acetyl group was observed in the vicinity of 1670 cm ⁻¹ , confirming the synthesis of a network polymer gel in which the ammonium salt was acetylated.

[Production of polymer gel electrolyte, measurement of conductivity]
The network polymer obtained in Synthesis Example 1 and Synthesis Example 38 was immersed in a 1M LiBF ₄ / EC 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. The ionic conductivity was measured at temperatures of 25 ° C. and 50 ° C., respectively.
The results are shown in Table 7.

* Content of electrolytic solution (wt%) = [(weight of electrolytic solution in polymer) / (polymer weight)] × 100
* EC: Ethylene carbonate

Ionic conductivity was measured using the network polymer gel obtained in Synthesis Examples 14, 15, and 39. Table 8 shows the results of immersing in an electrolyte solution of LiPF ₆ / EC (1M) and then measuring the ionic conductivity at measurement temperatures of 25 ° C. and 50 ° C.

The ionic conductivity of the network polymer gel obtained in Synthesis Example 15 was 3.95 × 10 ⁻⁴ S / cm at a measurement temperature of 25 ° C. and 4.95 × 10 ⁻⁴ S / cm at 50 ° C. Since the electrolyte solution was taken in more than the obtained network polymer, it increased significantly. The ionic conductivity of the network polymer obtained in Synthesis Example 39 was measured by adjusting the amount of the electrolytic solution. When the content of the electrolytic solution with respect to the polymer was 170%, it was 1.18 × 10 ⁻³ S / cm at a measurement temperature of 25 ° C. and 1.48 × 10 ⁻³ S / cm at 50 ° C., and was obtained in Synthesis Example 16. Compared with network polymer, ionic conductivity was improved. Further, the ionic conductivity of the network polymer obtained in Synthesis Example 39 is 4.16 × 10 ⁻³ S / cm at a measurement temperature of 50 ° C. when the content of the electrolytic solution is 100%. The value was similar to that of the network polymer obtained in Example 16. From these results, it is considered that by acetylating ammonium salt, the degree of freedom of the crosslinking point increased and the mobility of the network polymer increased.

[Tensile test of network polymer]
The network polymers obtained in Synthesis Example 1 and Synthesis Example 38 were each formed into a film having a thickness of about 100 μm, and cut into strips of 20 mm length × 3 mm width to obtain test pieces.
The tensile test was performed using a small desktop testing machine (EZ Test; manufactured by Shimadzu Corporation). The upper and lower sides of the test piece were fixed with a gripping tool, and the distance between the gripping tools was 10 mm. A 50N pneumatic planar gripper was used as the gripper. The measurement conditions were room temperature and a tensile speed of 5 mm / min.
The results are shown in Table 9.

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

Claims

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 portion of the partial structure represented by the chain, 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.
Following 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 chain, a hydrocarbon group having 1 to 15 carbon atoms, Z -. represents a counter anion), or the following 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 network polymer having a unit (A), or a network polymer having a unit (B) derived from the unit (A) and a radical polymerizable monomer,
A network polymer in which the molar ratio ((I) / (II)) between the partial structure represented by the formula (I) and the partial structure represented by the formula (II) is 1/1 to 10/1 (however, The unit (A) is composed of a partial structure represented by the formula (I) and a partial structure represented by the formula (II), and does not have the unit (B)).
2. The molar ratio ((A) / (B)) between the unit (A) and the unit (B) derived from the radical polymerizable monomer is from 1/1 to 1/100. Network polymer.
2. The network polymer according to claim 1, wherein the partial structure represented by the formula (I) is a structure represented by the following 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 4-position of the benzene ring. N2 is the same as defined in formula (I). .)
The network polymer according to claim 1, wherein the partial structure represented by the formula (II) is a structure represented by the following formula (IV).

(In the formula, y represents an integer of 1 to 12, and Z − represents a counter anion.)
The radical polymerizable monomer is one or more compounds selected from the group consisting of methyl methacrylate, n-butyl methacrylate, 2-hydroxyethyl methacrylate, polyethylene glycol methacrylate, styrene and acrylonitrile. The network polymer according to claim 1.
Formula (V)

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 The chain represents a hydrocarbon group having 1 to 15 carbon atoms, and X 1 and X 2 are the same or different and represent a group that acts as a bonding site during the polymerization reaction, and n1 represents an integer of 3 or 4.) A cyclic compound represented by:
Following formula (VI)

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 The chain represents a hydrocarbon group having 1 to 15 carbon atoms, and X 3 and X 4 are the same or different and each represents a group that acts as a binding site during the polymerization reaction, and Z − represents a counter anion). A structure in which the partial structure represented by the formula (II) is included in a skewered manner in the cyclic part of the partial structure represented by the formula (I) The method for producing a network polymer according to claim 1, wherein the compound having the structure (A) is polymerized after the compound having A) is formed.
Formula (VII) below

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 The chain represents a hydrocarbon group having 1 to 15 carbon atoms, and X 1 and X 2 are the same or different and each represents a group that acts as a binding site during a polymerization reaction or a group that does not act as a binding site during a polymerization reaction, provided that When n2 is 1, it is limited to the case where X 1 and X 2 are groups acting as a binding site during the polymerization reaction.
n1 represents an integer of 3 or 4. n2 represents an integer of 1 to 30. And a cyclic compound represented by
Following formula (VI)

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 The chain represents a hydrocarbon group having 1 to 15 carbon atoms, and X 3 and X 4 are the same or different and each represents a group that acts as a binding site during the polymerization reaction, and Z − represents a counter anion). Reaction with a linear compound
After generating the compound having the structure (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), The method for producing a network polymer according to claim 1, wherein the compound having the structure (A) and a radically polymerizable monomer are radically polymerized.
After polymerization, the obtained network polymer is further reacted with an electrophile,
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 A partial structure represented by the formula (II ′): a chain of a hydrocarbon group having 1 to 15 carbon atoms, and Z − represents a counter anion.

(Wherein R 3 and R 4 are the same as defined in formula (II), and R 5 represents a residue derived from an electrophile). Item 8. A method for producing a network polymer according to Item 6 or 7.
A polymer gel electrolyte comprising the network polymer according to any one of claims 1 to 5 in an electrolytic solution.
The polymer gel electrolyte according to claim 9, wherein the electrolytic solution is a propylene carbonate solution or an ethylene carbonate solution of lithium hexafluorophosphate or lithium tetrafluoroborate.
A secondary battery using the polymer gel electrolyte according to claim 9.