WO2012074089A1

WO2012074089A1 - Ionic gelling agent, gel, process for production of gel, and crosslinking agent

Info

Publication number: WO2012074089A1
Application number: PCT/JP2011/077911
Authority: WO
Inventors: 高崎幹大; 岩井良太; 吉田昌彦
Original assignee: 関東化学株式会社
Priority date: 2010-12-03
Filing date: 2011-12-02
Publication date: 2012-06-07
Also published as: JP2012117010A; JP5766942B2; CN103261330A; KR20130135858A; TW201231529A

Abstract

The purpose of the present invention is to provide: a gel which can overcome the disadvantages of conventional techniques, has high electrical conductivity, and does not cause the corrosion of a metal part of an electrochemical device or the like which is in contact with the gel; a gelling agent which can be used for the production of the gel; a gel production process which can produce the gel readily; and a crosslinking agent which can be used in the production of the gel. A gel produced using a gelling agent that comprises a specific crosslinking agent and a polymeric compound having an atom capable of forming an onium salt is found, whereby the purpose can be achieved.

Description

Ionic gelling agent, gel, method for producing gel and crosslinking agent

The present invention relates to an ionic gelling agent, a gel, a gel production method, and a crosslinking agent.

In recent years, gels have attracted attention in a wide range of fields, from basic research on structure and physical properties to applied research on foods, pharmaceuticals, cosmetics, and batteries. Electrolytic solution gelation technology is also attracting attention in the field of various electrochemical devices as a technology for preventing harmful electrolyte leakage that may cause chemical injury or explosion.

However, generally, when the electrolyte is gelled, there is a problem that the conductivity of the electrolyte is lowered. As a countermeasure, there is an attempt to improve the decrease in conductivity during gelation by imparting ionicity to the gelling agent.
As an ionic gel, a gel obtained by crosslinking a polymer with a polyvalent alkyl halide or an organic acid has been developed in the field of dye-sensitized solar cells (Patent Documents 1 to 3, Non-Patent Document 1).

However, the gels described in these documents have a problem in that a metal portion in contact with the gel in the electrochemical device is corroded by containing a high concentration of organic acid or halide ions.
Due to this problem, the lifetime of electrochemical devices is shortened, and the metal materials that can be used are limited, so that they can be applied only in specific fields and are insufficient for application in various fields of electrochemical devices. It was something.

JP 2001-160427 A JP2003-86258 JP2003-203520

In order to solve the above problems, the present inventors have intensively studied, and the gels described in Patent Documents 1 to 3 contain an organic acid or halide ion at a high concentration, so that an electrochemical device can be obtained. To solve these problems, focusing on the fact that the metal parts that come into contact with the gel are corroded, which lowers the durability of the electrochemical device and limits the metal materials that can be used. Thus, the inventors have found that the durability can be improved and a more versatile gel can be produced.
That is, an object of the present invention is to provide a gel that eliminates the problems of the prior art, retains conductivity, and does not corrode metal parts that come into contact with the gel in an electrochemical device or the like. Moreover, it is providing the gelling agent used for formation of the said gel, the manufacturing method of the gel for manufacturing the said gel easily, and the crosslinking agent for forming the said gel.

Based on the present situation as described above, the present inventors have made further studies and found that the above-described problem is caused by a specific crosslinking agent and a gelling agent containing a polymer compound having a nitrogen, phosphorus and / or sulfur atom. As a result of further research, the present inventors have completed the present invention.
That is, the present invention relates to the following.
(A) a gelling agent comprising a crosslinking agent and a polymer compound, which can form a network structure by forming an onium salt,
A plurality of substituents represented by the following formulas, in which the crosslinking agents may be the same or different

Where
R ¹ is independently selected from the group consisting of a fluoro group, a trifluoromethyl group, a pentafluoroethyl group, and a heptafluoropropyl group.
Having
Including saturated, unsaturated or aromatic hydrocarbons, which may contain heteroatoms,
The polymer compound includes one or more monomer units having one or more elements selected from the group consisting of N, P and S;
The gelling agent.

(B) The crosslinking agent has the following formula:

Where
R ^a and R ^b are each independently H or an alkyl group which may have a substituent,
m ₁ is an integer from 1 to 30,
m ₂ and m ₃ are each independently an integer of 0 to 15;
x is 2 or 3,
m ₄ is an integer from 0 to 15,
R ^c is an optionally substituted alkyl group having 1 to 20 carbon atoms,
y is an integer from 1 to 15,
z is an integer of 2 to 10,
Including one or more selected from the group consisting of compounds represented by:
The gelling agent as described in (a).

(C) The cross-linking agent has the following formula:

Where
m ₅ is an integer of 1 to 30,
Including one or more selected from the group consisting of compounds represented by:
The gelling agent according to (a) or (b).

(D) The gelling agent according to any one of (a) to (c), wherein the crosslinking agent has 2 to 5 substituents A.

(E) The polymer compound has the following formula:

Including one or more monomer units represented by:
Further, the polymer compound has the following formula:

Where
R ² and R ³ are independently of each other hydrogen or a methyl group;
D is a group having one or more elements selected from the group consisting of N, P and S;
E is an organic group,
When the carbon atom of the main chain to which the group D is bonded and the carbon atom of the main chain to which the group E is bonded are adjacent to each other, D and E may be bonded together with each carbon atom of the main chain to form a ring. Good,
1 type or 2 types or more selected from the group consisting of monomer units represented by
here,
When the monomer unit represented by the formula (11) is included, the equivalent ratio of the monomer unit represented by the formula (11) is 1 with respect to the equivalent ratio of the monomer unit represented by the formula (10). : 9-9: 1
The gelling agent according to any one of (a) to (d).

(F) the polymer compound has the following formula:

Where
n ₁ , n ₂ , n ₄ and n ₅ are each independently an integer of 1 to 10,
n ₃ is an integer from 0 to 10,
A is N (SO ₂ CF ₃ ) ₂ ,
R ⁴ represents a linear or branched alkyl group having 1 to 20 carbon atoms, an allyl group, a vinyl group, an optionally substituted benzyl group, an optionally substituted phenyl group, and carbon. Selected from the group consisting of linear or branched fluoroalkyl groups of 1 to 20;
Including one or more selected from the group consisting of monomer units represented by:
However, when any one of the formulas (18) to (20) is selected as a monomer unit, it contains at least one monomer of the formulas (12) to (17).
The gelling agent according to any one of (a) to (e).

(G) The gelling agent according to any one of (a) to (f), wherein the polymer compound has a number average molecular weight of 1,000 to 1,000,000.

(H) The gelling agent according to any one of (a) to (g), which gels a liquid medium containing an organic solvent, an ionic liquid and / or an electrolyte solution.

(I) The organic solvent is, for example, dimethylformamide (DMF), dimethylacetamide (DMA), dimethyl sulfoxide (DMSO), propylene carbonate (PC), ethylene carbonate (EC), dimethyl carbonate (DMC), γ-butyrolactone (GBL). ), Acetonitrile (AN), methoxypropionitrile (MPN), tetrahydrofuran (THF), toluene, methylene chloride, methoxyacetonitrile (MAN), N-methylpyrrolidinone (NMP), 2-methyltetrahydrofuran, 1,3-dioxane, 1,4-dioxane, anisole, monoglyme, propionitrile, 4-methyl-2-pentanone, butyronitrile, valeronitrile, benzonitrile, 1,2-dichloroethane, dimethoxyethane, methyl formate, ethyl acetate, pro Methyl onate, ethyl propionate, vinylene carbonate, 1,2-butylene carbonate, methyl ethyl carbonate, dimethylthioformamide, sulfolane, 3-methyl-sulfolane, trimethyl phosphate, triethyl phosphate, nitromethane, acetone, chloroform, dichloromethane and The gelling agent according to (h), which is one or more selected from the group consisting of carbon tetrachloride and the like.

(J) The organic solvent is dimethylacetamide (DMA), methoxyacetonitrile (MAN), N-methylpyrrolidinone (NMP), dimethylformamide (DMF), dimethylsulfoxide (DMSO), propylene carbonate (PC), ethylene carbonate (EC) , Γ-butyrolactone (GBL), acetonitrile (AN), methoxypropionitrile (MPN), acetone, chloroform, dichloromethane and carbon tetrachloride, one or more, (h) Or the gelling agent as described in (i).

(K) The ionic liquid includes a cation species and an anion species, and the cation may have a substituent, for example, an imidazolium ion, a pyridinium ion, a tetraalkylammonium ion, a pyrrolidinium ion, a pipette One or two or more selected from the group consisting of ridinium ion, tetraalkylphosnium ion, pyrazolium ion, trialkylsulfonium ion, morpholium ion, and guanidinium ion, and the anion is, for example, Halide ion (fluorine, chlorine, iodine, bromine), tetrafluoroborate ion (BF ₄ ⁻ ), hexafluorophosphate ion (PF ₆ ⁻ ), bis (trifluoromethanesulfonyl) imide ion (TFSA ⁻ ), thiocyanate ion (SCN ^-), nitrate ion (NO ₃ ⁻ ), sulfate ion (SO ₄ ²⁻ ), thiosulfate ion (S ₂ O ₃ ²⁻ ), carbonate ion (CO ₃ ²⁻ ), bicarbonate ion (HCO ₃ ⁻ ), phosphate ion, Phosphite ion, hypophosphite ion, halogen oxide ion (XO ₄ ⁻ , XO ₃ ⁻ , XO ₂ ^— or XO ⁻ , where X is fluorine, chlorine, bromine or iodine), halogen Acetate ion ((CX _n H _3-n ) COO ⁻ , where X is fluorine, chlorine, bromine or iodine and n is 1 to 3), tetraphenylborate ion (BPh ₄ ⁻ ) And derivatives thereof (B (Aryl) ₄ ^— , where Aryl = phenyl group having a substituent) and the like, or one or more thereof, described in (h) Gelling agent.

(L) The electrolyte solution is, for example, one or more selected from the group consisting of a solution containing iodine and iodide, a solution containing lithium ions, and a solution containing a tetraalkylammonium salt. The gelling agent as described in h).
(M) The gelling agent according to any one of (a) to (l), wherein the content of the polymer compound is 15 to 75% by weight based on the gelling agent.

(N) The gelling agent according to any one of (a) to (m), wherein the content of the crosslinking agent is 25 to 85% by weight based on the gelling agent.
(O) The gelling agent according to any one of (h) to (n), wherein the total content of the liquid medium is 0.1 to 50% by weight when the gel is formed.

(P) The gelling agent according to any one of (a) to (o), which is used for forming a gel used in a site in contact with an electrode.
(Q) A gel formed using the gelling agent according to any one of (a) to (p).

(R) A crosslinking agent used for forming the gelling agent according to any one of (a) to (p).
(S) A method for producing a gel using the gelling agent according to any one of (a) to (p),
The said method including the process of mixing a gelatinizer and a liquid medium.

According to the present invention, it is possible to provide a gel that solves the problems of the prior art, does not significantly lower the conductivity of the electrolyte, and does not corrode the metal part that contacts the gel. Furthermore, it is possible to provide a gelling agent used for forming the gel, a gel production method capable of easily producing the gel, and a crosslinking agent for forming the gel.

As a corrosion test, by LSV measurement, LiTFSA-PC solution, gel crosslinked with 1,12-dibromododecane, crosslinked with N, N, N ′, N′-tetra (trifluoromethanesulfonyl) -dodecane-1,12-diamine It is the anodic measurement result of the obtained gel.

Hereinafter, the ionic gelling agent, the gel, the method for producing the gel, and the crosslinking agent of the present invention will be described.
<Gelling agent>
The gelling agent of the present invention contains a crosslinking agent and a polymer compound. And these form gels by forming onium salts.
Here, the onium salt refers to a compound produced by a coordinate bond between a compound having an electron pair that does not participate in a chemical bond and another cationic compound.
For example, pyridine and alkylated TFSA react, and a cation of alkylpyridinium and an anion of TFSA are coordinated to form an onium salt to form a gel.

(Crosslinking agent)
First, the crosslinking agent will be described.
The crosslinking agent of the present invention has a plurality of substituents A represented by the following formula:

Where
R ¹ is independently of each other a fluoro group, or an alkyl group or an aryl group having a fluoro group, and the alkyl group or the aryl group may have a substituent.
Have
Including saturated hydrocarbons, unsaturated hydrocarbons or aromatic hydrocarbons, which may contain heteroatoms.

Such a cross-linking agent is capable of forming an onium salt with a polymer compound described later. Moreover, although such a crosslinking agent bridge | crosslinks from the substituent A as a base point, when a gel is formed as a result, a halide ion and an organic acid are not contained. Therefore, metal parts such as electrodes in contact with the gel are not corroded. Moreover, this crosslinking agent does not easily undergo a crosslinking reaction at room temperature. On the other hand, a crosslinking reaction easily proceeds by applying energy such as heating. Therefore, the gelling agent of the present invention can easily select the gel formation conditions. As a result, the production of the gel can be facilitated, for example, the gel formability can be improved.

Examples of saturated hydrocarbons include alkanes and cycloalkanes. The saturated hydrocarbon may have a substituent other than the substituent A, and may be linear or branched.
Examples of the unsaturated hydrocarbon include alkene, cycloalkene, alkyne, and cycloalkyne. The unsaturated hydrocarbon may have a substituent other than the substituent A, and may be linear or branched.
Examples of the aromatic hydrocarbon include benzene, biphenyl, naphthalene and anthracene. The aromatic hydrocarbon may have a substituent other than the substituent A.

R ¹ is not particularly limited as long as it is a fluoro group, or an alkyl group or aryl group having a fluoro group. Typically, the alkyl group having a fluoro group is a C 1-20 alkyl group having a fluoro group, preferably a C 1-10 alkyl group having a fluoro group, more preferably a fluoro group. And an alkyl group having 1 to 3 carbon atoms, more preferably a trifluoromethyl group, a pentafluoroethyl group, and a heptafluoropropyl group.
Examples of the substituent A include —N (SO ₂ F) ₂ , —N (SO ₂ CF ₃ ) ₂ , —N (SO ₂ C ₂ F ₅ ) ₂ , —N (SO ₂ C ₃ F ₇ ) ₂ , —N (SO ₂ CHF ₂ ) ₂ , —N (SO ₂ CH ₂ F) _{2 and the} like.

Among these, the substituent A is preferably —N (SO ₂ CF ₃ ) ₂ , —N (SO ₂ C ₂ F ₅ ) ₂ and —N (SO ₂ C) from the viewpoint of easy availability. ₃ F ₇ ) ₂ .
Examples of the substituent other than the substituent A include, but are not limited to, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, and an ester group having 1 to 30 carbon atoms. Be

The alkyl group, alkoxy group, and ester group may be further substituted with an amino group, a cyano group, or the like, and may be linear or branched.
Examples of the hetero atom include a nitrogen atom, a phosphorus atom, and a sulfur atom. Among the above, the hetero atom is preferably a nitrogen atom and a sulfur atom, more preferably a nitrogen atom, from the viewpoint of easy availability.

Specific examples of the crosslinking agent containing the saturated hydrocarbon, unsaturated hydrocarbon, or aromatic hydrocarbon include compounds represented by the following formulas (1) to (4).

R ^a and R ^b are each independently H or an alkyl group which may have a substituent.
m ₁ is an integer of 1 to 30, preferably 3 to 30, and more preferably 6 to 30. Within the above range, various liquid media can be gelled.

m ₂ and m ₃ are each independently an integer of 1 to 30, preferably 1 to 10, and more preferably 2 to 5.
x is 2 or 3, preferably 3.
m ₄ is an integer of 1 to 15, preferably 1 to 10, and more preferably 2 to 5.

R ^c is an optionally substituted alkyl group having 1 to 20 carbon atoms, and among these, 1 to 10 is preferable, and 1 to 5 is more preferable.
y is an integer of 1 to 15, preferably 3 to 15.

z is an integer of 2 to 10, and preferably 4 to 10 from the viewpoint of gelation ability.
The substituent is not particularly limited, and examples thereof include an alkyl group having 1 to 10 carbon atoms, an alkoxy group, an ester group, a thiol group, a sulfide group, an amide group, and an imide group. The alkyl group, alkoxy group, ester Group, thiol group, sulfide group, amide group and imide group may further have a substituent such as alkyl group, alkoxy group, ester group, thiol group, sulfide group, amide group and imide group, May be linear or branched.

Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group.
Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, and a tert-butoxy group.

More preferable examples of the saturated hydrocarbon, unsaturated hydrocarbon, or aromatic hydrocarbon include compounds represented by the following formulas (5) to (9).

m ₅ is an integer of 1 to 30, preferably 3 to 20, and more preferably 6 to 15.
The number of substituents A contained in the above-mentioned saturated hydrocarbon, unsaturated hydrocarbon or aromatic hydrocarbon contained in the crosslinking agent is 2 to 30 and is not particularly limited, but is preferably from the viewpoint of easy synthesis. Is 2-5.
The content of the crosslinking agent with respect to the gelling agent is not particularly limited, but is 25 to 85% by weight. From the viewpoint of electrical conductivity, it is preferably 25 to 50% by weight, and more preferably 25 to 30% by weight. It is.

(Polymer compound)
Next, the polymer compound will be described.
The polymer compound includes a monomer unit having one or two or more elements selected from the group consisting of N, P and S.

Such a polymer compound is not particularly limited as long as it includes the above-described monomer unit. For example, the following formula:

It can contain 1 type, or 2 or more types of monomer units represented by these.
Such a polymer compound is suitably crosslinked by the above-described crosslinking agent.

In the formula, R ² is hydrogen or a methyl group, and D is a group having one or more elements selected from the group consisting of N, P and S.
From the viewpoint of easy availability, D described above is preferably a group having a nitrogen atom.
Examples of the monomer unit of the formula (10) include a vinylpyridine unit, a vinylpyrrolidine unit, a vinylpyrrole unit, a vinyldimethylamine unit, a vinylimidazole unit, a dimethylaminoalkylacrylate unit, a dimethylaminoalkylmethacrylate unit, and a dimethylaminoalkylacrylamide unit. Vinyl phosphine unit, vinyl thiophene unit, vinyl sulfide unit and the like. The monomer unit may have a substituent.

Examples of the substituent include, but are not limited to, an alkyl group having 1 to 30 carbon atoms, an alkoxy group, an ester group, a thiol group, a sulfide group, an amide group, and an imide group. , Alkoxy groups, ester groups, thiol groups, sulfide groups, amide groups and imide groups have further substituents such as alkyl groups, alkoxy groups, ester groups, thiol groups, sulfide groups, amide groups and imide groups. It may also be linear or branched.

Among the monomer units represented by the above formula (10), from the viewpoint that gelation is easy, the following formula:

The monomer unit represented by formula (12), (13) and (15) is more preferred.

In formula (14), n ₁ is an integer of 1 to 10, and is preferably 1 to 5 and more preferably 2 to 3 from the viewpoint of easy availability.
In formula (15), n ₂ is an integer of 1 to 10, and is preferably 1 to 5 and more preferably 2 to 3 from the viewpoint of easy availability.

In the formula (16), n ₃ is an integer of 0 to 10, and is preferably 1 to 5, more preferably 2 to 3, from the viewpoint of easy availability.
The high molecular compound may be comprised including monomer units other than the said monomer unit.
For example, the polymer compound has the following formula:

1 type or 2 or more types of monomer units represented by these may be further included.

In the formula, R ³ is hydrogen or a methyl group, and E is an organic group. Examples of E include an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a hydroxyl group, a sulfide group, an ester group, an aryl group, and a heteroaryl group, and these may have a substituent. It may also be linear or branched.
Of these, an alkyl group and a quaternary heteroaryl group are preferable from the viewpoint of solubility in a solvent.

Among the monomer units represented by the formula (11), from the viewpoint of improving the solubility in an organic solvent and the gelling ability, the following formula:

Is preferred.

In formula (18), n ₄ is an integer of 0 to 10, and is preferably 0 to 2 and more preferably 0 from the viewpoint of easy availability.
In formula (19), n ₅ is an integer of 1 to 10, preferably 1 to 6, and more preferably 1 to 3.
A is N (SO ₂ CF ₃ ) ₂ .

Examples of R ⁴ include an alkyl group, an alkenyl group, an alkynyl group, and an aryl group, which may have a substituent and / or a hetero atom.
Among these, R ⁴ preferably has a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, an allyl group, a vinyl group, or a substituent from the viewpoint of easy availability. A benzyl group which may be substituted, an aryl group which may have a substituent, and a linear, branched or cyclic fluoroalkyl group having 1 to 30 carbon atoms.

The cross-linking reaction proceeds well without depending on the number of n ₄ and n ₅ .
When the polymer compound includes a monomer unit represented by the formula (10) and further includes a monomer unit represented by the formula (11), the monomer units of the formula (10) and the formula (11) are Any of the following four types of bonds may be used.

Further, it preferably contains at least a monomer unit represented by the formula (12), and further contains one or more selected from the group consisting of the formulas (18), (19) and (20).
However, when any one of the formulas (18) to (20) is selected as the monomer unit, at least one monomer of the formulas (12) to (17) is included.

When the carbon atom of the main chain to which the group D is bonded and the carbon atom of the main chain to which the group E is bonded are adjacent to each other, D and E may be bonded together with each carbon atom of the main chain to form a ring. Well, the monomer unit is not particularly limited, but for example, the following formula:

It is represented by

The monomer unit represented by the formula (11) is equivalent to the monomer unit represented by the formula (10) in an equivalent ratio of 1: 9 to 9: 1, which is preferable from the viewpoint of easy crosslinking reaction. Is from 1: 9 to 5: 5, more preferably from 3: 7 to 5: 5.
The number average molecular weight of the polymer compound is not particularly limited, but is 1,000 to 1,000,000, and from the viewpoint of polymer solubility, it is 10,000 to 200,000, more preferably 10,000. ~ 100,000.

The copolymer type of the high molecular compound is not particularly limited, and may be, for example, a block copolymer, a graft copolymer, a random copolymer, an alternating copolymer, a periodic copolymer, or a combination thereof. Good.
The weight ratio of the crosslinking agent to the polymer compound is not particularly limited, but is preferably 1: 2 to 1:30, more preferably 1: 2 to 1:10, from the viewpoint of gelation speed. .

As mentioned above, since the gelatinizer of this invention has ionicity after gel formation, it has electroconductivity. Moreover, since the gelling agent of the present invention does not by-produce halide ions or organic acids during gel formation, it does not promote the corrosion of the metal part in contact with the gel. Therefore, when the gel formed with the said gelling agent is applied, there exists an effect of enabling manufacture of the device excellent in durability. In addition, the gelling agent of the present invention can gel an extremely wide variety of liquid media. Furthermore, the gelling agent of the present invention can form a gel having high thermal stability and transparency. Furthermore, since the reaction of the gelling agent of the present invention is suppressed at room temperature, unintentional gelation can be prevented. Moreover, since gelation can be easily performed by heating or the like, it is excellent in gel moldability.
Moreover, the gelling agent may contain components other than the component mentioned above.

<Gel>
The gel of the present invention formed using the gelling agent as described above will be described. The gel of the present invention is formed using the above-described gelling agent and a liquid medium.
As the gelling agent, those described above can be used alone or in combination of two or more.

Although the liquid medium (liquid medium) gelatinized by the gelatinizer of this invention is not specifically limited, For example, various liquid inorganic substances, an organic solvent, or an ionic liquid can be used. Among these, one or a combination of two or more can be used, and the liquid medium can be suitably gelled.
Examples of the liquid inorganic material include water.

Examples of the organic solvent include dimethylformamide (DMF), dimethylacetamide (DMA), dimethyl sulfoxide (DMSO), propylene carbonate (PC), ethylene carbonate (EC), dimethyl carbonate (DMC), γ-butyrolactone (GBL), Acetonitrile (AN), methoxypropionitrile (MPN), tetrahydrofuran (THF), toluene, methylene chloride, methoxyacetonitrile (MAN), N-methylpyrrolidinone (NMP), 2-methyltetrahydrofuran, 1,3-dioxane, 1, 4-dioxane, anisole, monoglyme, propionitrile, 4-methyl-2-pentanone, butyronitrile, valeronitrile, benzonitrile, 1,2-dichloroethane, dimethoxyethane, methyl formate, ethyl acetate, Methyl pionate, ethyl propionate, vinylene carbonate, 1,2-butylene carbonate, methyl ethyl carbonate, dimethylthioformamide, sulfolane, 3-methyl-sulfolane, trimethyl phosphate, triethyl phosphate, nitromethane, acetone, chloroform, dichloromethane and Examples include carbon tetrachloride. From the viewpoint of conductivity, preferably, dimethylacetamide (DMA), methoxyacetonitrile (MAN), N-methylpyrrolidinone (NMP), dimethylformamide (DMF), dimethylsulfoxide (DMSO), propylene carbonate (PC), ethylene carbonate ( EC), γ-butyrolactone (GBL), acetonitrile (AN), methoxypropionitrile (MPN), acetone, chloroform, dichloromethane and carbon tetrachloride.

Examples of the ionic liquid include a cation species and an anion species, and the cation may have a substituent, such as an imidazolium ion, a pyridinium ion, a tetraalkylammonium ion, a pyrrolidinium ion, and a piperidinium ion. , A tetraalkylphosnium ion, a pyrazolium ion, a trialkylsulfonium ion, a morpholium ion, and a guanidinium ion, and the anion is a halide ion (fluorine). , Chlorine, iodine, bromine), tetrafluoroborate ion (BF ₄ ⁻ ), hexafluorophosphate ion (PF ₆ ⁻ ), bis (trifluoromethanesulfonyl) imide ion (TFSA ⁻ ), thiocyanate ion (SCN ⁻ ), nitrate ion (NO ₃ ), Sulfate ion _(SO ^{4 2-),} thiosulfate _(S ^{₂ O 3 2-),} carbonate ions _(CO ^{3 2-),} bicarbonate ions (HCO ₃ ^-), phosphate ion, phosphite ion, Hypophosphite ion, halogen oxide ion (XO ₄ ⁻ , XO ₃ ⁻ , XO ₂ ^— or XO ⁻ , where X is fluorine, chlorine, bromine or iodine), halogenated acetate ion (( CX _n H _3-n ) COO ⁻ , where X is fluorine, chlorine, bromine or iodine, and n is 1 to 3), tetraphenylborate ion (BPh ₄ ⁻ ) and its derivatives ( B (Aryl) ₄ ^— , where Aryl = phenyl group having a substituent.

Examples of the electrolyte solution include a solution containing iodine and iodide, a solution containing lithium ions, a solution containing a tetraalkylammonium salt, and a solution containing an ionic liquid. Of these, a solution containing iodine and iodide, a solution containing lithium ions, and a solution containing a tetraalkylammonium salt are preferable.

The liquid medium may include one or more selected from the group consisting of nitrile solvents such as acetonitrile and methoxypropionitrile, γ-butyrolactone, propion carbonate, and propylmethylimidazole iodide among the above-mentioned. preferable.
The total content of the liquid medium in the gel is not particularly limited, but is 200 to 100,000 parts by weight, preferably 1,000 to 5,000 parts by weight with respect to 100 parts by weight of the gelling agent. is there. When the total content of the liquid medium is within the above range, gel formation proceeds well.

In the embodiment of the present invention, the gel contains a conductive substance. The conductive substance contributes to the improvement of the conductivity of the gel, and examples thereof include an electrolyte and conductive fine particles.
The electrolyte improves conductivity by being dissolved in a liquid medium. Examples of such an electrolyte include, but are not limited to, iodine and iodide, lithium salt, tetraalkylammonium salt, and the like, and may include one or more.

Further, the conductive particles are present in a dispersed manner in the liquid medium, and are not particularly limited as long as they impart conductivity to the liquid medium.

Since the gelling agent has ionicity after the gel is formed, the gel of the present invention has conductivity even without a conductive substance.

Since the above-described gel does not release halogen ions in the gel, it suppresses corrosion of metal parts in electrochemical devices and the like. Therefore, it can be used for a portion in contact with an electrode or the like.
The gel described above can be used for, for example, photovoltaic power generation, a lithium ion battery, and an electric double layer capacitor.

<Method for producing gel>
Next, a method for producing a gel using the gelling agent of the present invention will be described.
The manufacturing method of the gel of this invention includes the process of mixing the gelatinizer mentioned above and a liquid medium. In this embodiment, the process of further heating is included.

In the above method, the mixing method is not particularly limited. For example, the polymer compound and the liquid medium may be mixed with the gelling agent, or the crosslinking agent and the liquid medium may be mixed with the polymer compound. Good.
In the above method, the heating temperature is not particularly limited, but it is preferably 40 to 120 ° C., more preferably 40 to 80 ° C. in consideration of economy and reactivity. When the heating temperature is within the above range, gel formation proceeds well.

In the said method, the gel mentioned above can be manufactured according to content of a crosslinking agent, a high molecular compound, and a liquid medium.
In the method for producing the gel of the present invention, the cross-linking reaction is unlikely to proceed at room temperature, but can be suitably gelled by heating or the like. Therefore, the cross-linking reaction can be controlled, and the gel can be easily molded. As a result, the reaction proceeds rapidly at room temperature due to the high reactivity of the alkyl halide, and further, it is difficult to fill the obtained gel into a cell or the like according to each application due to the progress of this rapid reaction. The problem described in Non-Patent Document 1 does not occur. Therefore, the production method described above can be used as a method for producing a gel for electrochemical devices in a wide range of fields.

By the way, in the formation of the gel, the details of the mechanism of the cross-linking reaction between the cross-linking agent and the polymer compound are not clear, but cross-linking occurs by forming an onium salt by the following reaction, and a network-structured gel is formed. It is thought that.
An example of this polymerization reaction is shown below.
TFSA represents N (SO ₂ CF ₃ ) ₂ and Ph represents a phenyl group.

In the above reaction formula (I), poly (4-vinylpyridine), which is a compound having two or more atomic groups containing nitrogen atoms, and an organic compound having two bis (trifluoromethanesulfonamide) groups per molecule This shows a reaction of synthesizing a polymer composed of a crosslinked onium salt containing N by addition reaction with N, N, N ′, N′-tetra (trifluoromethanesulfonyl) -dodecane-1,12-diamine. .

In the above reaction formula (II), poly (vinylphenyldiphenylphosphine) which is a compound having two or more atomic groups containing phosphorus atoms per molecule and an organic compound having two bis (trifluoromethanesulfonamide) groups per molecule This shows a reaction for synthesizing a polymer composed of a crosslinked onium salt containing P by addition reaction with N, N, N ′, N′-tetra (trifluoromethanesulfonyl) -dodecane-1,12-diamine. .

In the above reaction formula (III), poly (4-vinylphenylphenyl sulfide), which is a compound having two or more atomic groups containing sulfur atoms, and two bis (trifluoromethanesulfonamide) groups per molecule are used. Reaction for synthesizing a polymer comprising a crosslinked onium salt containing S by addition reaction with an organic compound N, N, N ′, N′-tetra (trifluoromethanesulfonyl) -dodecane-1,12-diamine Indicates.

As mentioned above, although this invention was demonstrated based on the preferred embodiment of this invention, this invention is not limited to this.
The present invention can be used in combination with any configuration described above. For example, the crosslinking agent of the present invention may be the same or different, and a plurality of substituents A represented by the following formula:

Where
R ¹ is independently selected from the group consisting of a trifluoromethyl group, a pentafluoroethyl group, and a heptafluoropropyl group.
Having
What is necessary is just to contain the saturated hydrocarbon, unsaturated hydrocarbon, or aromatic hydrocarbon which may contain the hetero atom, and is not limited to the crosslinking agent mentioned above.

Further, for example, the polymer compound of the present invention only needs to contain a monomer unit having one or more elements selected from the group consisting of N, P and S, and is limited to the above-described polymer compound. Not.
In the method for producing a gel of the present invention, crosslinking may be performed by light energy such as UV, pressure or the like instead of heating.

Next, the present invention will be specifically described based on the following examples, but the present invention is not limited thereto.
[Examples 1 to 18] Gelation test As gelling agents, the following crosslinking agents and polymer compounds were prepared in combinations shown in Table 1.

Cross-linking agent :
N, N, N ′, N′-tetra (trifluoromethanesulfonyl) -propane-3-diamine (TFSA- (CH ₂ ) ₃ -TFSA)
N, N, N ′, N′-tetra (trifluoromethanesulfonyl) -hexane-6-diamine (TFSA- (CH ₂ ) ₆ -TFSA)
N, N, N ′, N′-tetra (trifluoromethanesulfonyl) -dodecane-1,12-diamine (TFSA- (CH ₂ ) ₁₂ -TFSA)
N, N, N ′, N′-tetra (trifluoromethanesulfonyl) -p-xylenediamine (TFSA—CH ₂ —Ph—CH ₂ —TFSA)
N, N, N ′, N ′, N ″, N ″ -hexa (trifluoromethanesulfonyl) -N ′ ″, N ′ ″, N ′ ″-tris (aminoethyl) amine (N (C ₂ H ₄ -TFSA) ₃ )

Polymer compound :
Poly (4-vinylpyridine) (P4VP, molecular weight: 60,000)
Poly (4-vinylpyridine-co-4-vinyl-N-allyl-pyridium bis (trifluoromethanesulfonyl) amide) (P4VP-Allyl, molecular weight: 60,000)
Poly (N-vinyl-imidazole) (PVIm)
Poly (diallylamine) (PDAMA)
Poly (dimethylaminoethyl methacrylate) (PDMAEMA)
The gel was prepared by mixing and heating the above-mentioned gelling agent and the following liquid medium.

Liquid medium :
Dimethyl sulfoxide (DMF)
Dimethylformamide (DMSO)
Propylene carbonate (PC)
Ethylene carbonate (EC)
γ-Butyrolactone (GBL)
Acetonitrile (AN)
Toluene
Chloroform (CHCl ₃ )
Acetone
Dimethyl carbonate (DMC)
Iodine / lithium iodide / tert-butylpyridine (I ₂ / LiI / t-BuPy)
Tetraethylammonium borofluoride (NEt ₄ BF ₄ )
Lithium bis (trifluoromethanesulfonyl) amide (LiTFSA)
Propylmethylimidazolium iodide (PMImI)
Allylbutylimidazolium bis (trifluoromethanesulfonylamide) (ABImTFSA)

As an example of the preparation of the gel by the combination of the gelling agent and the liquid medium (Table 1) described above, the preparation methods of Examples 1, 9, 17 and 18 are shown below.
[Example 1]
50 mg (0.47 mmol) of poly (4-vinylpyridine) (P4VP) (molecular weight: 60,000) is dissolved in 0.5 mL of DMF, and N, N, N ′, N′-tetra (trifluoromethanesulfonyl) -propane-3- Diamine (TFSA- (CH ₂ ) ₃ -TFSA) 50 mg (0.05 mmol) was mixed. The sample was heated to 80 ° C. and a gel sample was obtained after 30 minutes.
[Example 9]
50 mg (0.26 mmol) of poly (dimethylaminoethyl methacrylate) (PDMAEMA) is dissolved in 0.5 mL of toluene, and N, N, N ′, N′-tetra (trifluoromethanesulfonyl) -dodecane-1,12-diamine ( 12.5 mg (0.02 mmol) of TFSA- (CH ₂ ) ₁₂ -TFSA) was mixed. A sample of gel was obtained after 30 minutes of heating to 80 ° C.

[Example 17]
20 mg (0.19 mmol) of poly (4-vinylpyridine) (P4VP) is dissolved in 0.5 mL of allylbutylimidazolium bis (trifluoromethanesulfonylamide), and N, N, N ′, N′-tetra (trifluoromethanesulfonyl) is dissolved. ) -Dodecane-1,12-diamine (TFSA- (CH ₂ ) ₁₂ -TFSA) 12.5 mg (0.02 mmol) was mixed. After heating to 100 ° C., a white opaque gel was obtained after 30 minutes.
[Example 18]
20 mg (0.11 mmol) of poly (dimethylaminoethyl methacrylate) (PDMAEMA) is dissolved in 0.5 mL of allylbutylimidazolium bis (trifluoromethanesulfonylamide), and N, N, N ′, N′-tetra (trifluoromethanesulfonyl) is dissolved. ) -Dodecane-1,12-diamine (TFSA- (CH ₂ ) ₁₂ -TFSA) 12.5 mg (0.02 mmol) was mixed. After heating to 100 ° C., a transparent gel was obtained after 30 minutes.

[Results of Examples 1 to 18]

Blending ratio = (number of moles of crosslinking agent) / (number of moles of monomer units contained in the polymer compound)
Calculated as
As shown in Table 1, the gelling agent of the present invention as described above was able to suitably gel various liquid media.

[Examples 19 to 23] Conductivity test [Example 19]
50 mg (0.45 mmol) of polydiallylmethylamine (PDAMA) was dissolved in 0.5 mL of AN solution of I ₂ / LiI 0.01 mol / L / 0.1 mol / L, and N, N, N ′, N′− 25 mg (0.04 mmol) of tetra (trifluoromethanesulfonyl) -dodecane-1,12-diamine (TFSA- (CH ₂ ) ₁₂ -TFSA) was mixed. The sample was heated to 80 ° C. and a gel sample was obtained after 30 minutes.

[Example 20]
50 mg (0.47 mmol) of poly (4-vinylpyridine) (P4VP, molecular weight: 60,000) was dissolved in 0.5 mL of a GBL solution of I ₂ / LiI 0.01 mol / L / 0.1 mol / L, and N, N, 25 mg (0.04 mmol) of N ′, N′-tetra (trifluoromethanesulfonyl) -dodecane-1,12-diamine (TFSA— (CH ₂ ) ₁₂ —TFSA) was mixed. The sample was heated to 80 ° C. and a gel sample was obtained after 30 minutes.

[Example 21]
A solution of 50 mg (0.47 mmol) of poly (4-vinylpyridine-co-vinyl-N-allylpyridinium bis (trifluoromethanesulfonyl) amide) (P4VP-Allyl, molecular weight 60,000) in I ₂ 0.01 mol / L AN solution 0. Dissolved in 5 mL, mixed with 25 mg (0.03 mmol) of N, N, N ′, N′-tetra (trifluoromethanesulfonyl) -dodecane-1,12-diamine (TFSA- (CH ₂ ) ₁₂ -TFSA). After heating to 80 ° C., a transparent gel was obtained after 30 minutes.

[Example 22]
50 mg (0.45 mmol) of poly (diallylmethylamine) (PDAMA) was dissolved in 0.5 mL of an AN solution of 0.01 mol / L of I ₂ , and N, N, N ′, N′-tetra (trifluoromethanesulfonyl)- 25 mg (0.03 mmol) of dodecane-1,12-diamine (TFSA- (CH ₂ ) ₁₂ -TFSA) was mixed. After heating to 80 ° C., a transparent gel was obtained after 30 minutes.

[Example 23]
25 mg (0.24 mmol) of poly (4-vinylpyridine) (P4VP, molecular weight: 60,000) was dissolved in 0.5 mL of a PC solution of LiTFSA 1.0 mol / L, and N, N, N ′, N′-tetra (trifluoro) 12.5 mg (0.02 mmol) of romethanesulfonyl) -dodecane-1,12-diamine (TFSA- (CH ₂ ) ₁₂ -TFSA) was mixed. After heating to 80 ° C., a transparent gel was obtained after 30 minutes.

[Reference Examples 1 to 4]
As a reference example, an electrolytic solution shown in Table 2 below was prepared, and conductivity was measured.

[Comparative Example 1]
50 mg (0.47 mmol) of poly (4-vinylpyridine) (P4VP, molecular weight: 60,000) was dissolved in 0.5 mL of a GBL solution of I ₂ / LiI 0.01 mol / L / 0.1 mol / L, and 1,12- Dibromododecane (Br— (CH ₂ ) ₁₂ —Br) 13.1 mg (0.03 mmol) was mixed. After heating to 80 ° C., a transparent gel was obtained after 30 minutes.

[Comparative Example 2]
A solution of 50 mg (0.47 mmol) of poly (4-vinylpyridine-co-vinyl-N-allylpyridinium bis (trifluoromethanesulfonyl) amide) (P4VP-Allyl, molecular weight 60,000) in I ₂ 0.01 mol / L AN solution 0. Dissolved in 5 mL, mixed with 13.1 mg (0.03 mmol) of 1,12-dibromododecane (Br— (CH ₂ ) ₁₂ —Br). After heating to 80 ° C., a transparent gel was obtained after 30 minutes.

Tables 2 and 3 show the results of measuring the impedance of each sample at a temperature of 27 ° C. and a frequency of 10 ⁶ → 10 ⁻¹ (Modola, Toyo Technica) and comparing the results with the corresponding reference examples. In addition,
Conductivity maintenance rate (%) = (impedance of each example / impedance of each reference example) × 100 (%)
Calculated as

As shown in Table 3, the result that no significant decrease in conductivity was observed during gelation was obtained. Moreover, as shown in Tables 3 and 4, it was shown that the gel formed by the gelling agent of the present invention can maintain higher conductivity than the gels of Comparative Examples 1 and 2.

[Example 24] Corrosion test The corrosion test was carried out by measuring the corrosion potential of the metal used for the electrode in the following three kinds of gels.

The gel samples are as shown in Table 5.

Experimental Method LSV measurement (working electrode: aluminum, counter electrode: platinum, reference electrode: Ag / Ag ⁺ AN) was performed using a potentiostat (Hokuto Denko HSV-100). FIG. 1 shows the results of anode measurement in

samples

1, 2 and 3. In the case of the gel containing bromide of sample 2, since it was greatly oxidized at +2 V, it was revealed that the aluminum electrode was corroded by bromide ions. On the other hand, Sample 1 and Sample 3 (gel containing TFSA ions) overlap each other, and it was confirmed that the electrode was not oxidized under these conditions.
Thus, it was shown that the gel formed using the gelling agent of the present invention is more advantageous in terms of electrode corrosion than the gel containing halogen.

The gel formed by the gelling agent of the present invention does not promote the corrosion of the metal part in contact with the gel in the electrochemical device while maintaining high conductivity, and therefore is used for various electrochemical devices. It can be applied to the solidification use of the electrolyte solution.

Claims

A gelling agent comprising a crosslinking agent and a polymer compound, which can form a network structure by forming an onium salt,
A plurality of substituents represented by the following formulas, in which the crosslinking agents may be the same or different

Where
R 1 is independently selected from the group consisting of a trifluoromethyl group, a pentafluoroethyl group, and a heptafluoropropyl group.
Having
Including saturated, unsaturated or aromatic hydrocarbons, which may contain heteroatoms,
The polymer compound includes one or more monomer units having one or more elements selected from the group consisting of N, P and S;
The gelling agent.
The crosslinking agent has the following formula:

Where
R a and R b are each independently H or an alkyl group which may have a substituent,
m 1 is an integer from 1 to 30,
m 2 and m 3 are each independently an integer of 0 to 15;
x is 2 or 3,
m 4 is an integer from 0 to 15,
R c is an optionally substituted alkyl group having 1 to 20 carbon atoms,
y is an integer from 1 to 15,
z is an integer of 2 to 10,
Including one or more selected from the group consisting of compounds represented by:
The gelling agent according to claim 1.
The crosslinking agent has the following formula:

Where
m 5 is an integer of 1 to 30,
Including one or more selected from the group consisting of compounds represented by:
The gelling agent according to claim 1 or 2.
The gelling agent according to any one of claims 1 to 3, wherein the crosslinking agent has 2 to 5 substituents A.
The polymer compound has the following formula:

Including one or more monomer units represented by:
Further, the polymer compound has the following formula:

Where
R 2 and R 3 are independently of each other hydrogen or a methyl group;
D is a group having one or more elements selected from the group consisting of N, P and S;
E is an organic group,
When the carbon atom of the main chain to which the group D is bonded and the carbon atom of the main chain to which the group E is bonded are adjacent to each other, D and E may be bonded together with each carbon atom of the main chain to form a ring. Good,
1 type or 2 types or more selected from the group consisting of monomer units represented by
here,
When the monomer unit represented by the formula (11) is included, the equivalent ratio of the monomer unit represented by the formula (11) is 1 with respect to the equivalent ratio of the monomer unit represented by the formula (10). : 9-9: 1
The gelling agent according to any one of claims 1 to 4.
The polymer compound has the following formula:

Where
n 1 , n 2 , n 4 and n 5 are each independently an integer of 1 to 10,
n 3 is an integer from 0 to 10,
A is N (SO 2 CF 3 ) 2 ,
R 4 represents a linear or branched alkyl group having 1 to 20 carbon atoms, an allyl group, a vinyl group, an optionally substituted benzyl group, an optionally substituted phenyl group, and carbon. Selected from the group consisting of linear or branched fluoroalkyl groups of 1 to 20;
Including one or more selected from the group consisting of monomer units represented by:
However, when any one of the formulas (18) to (20) is selected as a monomer unit, it contains at least one monomer of the formulas (12) to (17).
The gelling agent according to any one of claims 1 to 5.
The gelling agent according to any one of claims 1 to 6, wherein the polymer compound has a number average molecular weight of 1,000 to 1,000,000.
The gelling agent according to any one of claims 1 to 7, which gels a liquid medium containing an organic solvent, an ionic liquid and / or an electrolyte solution.
Organic solvents are dimethylformamide (DMF), dimethylacetamide (DMA), dimethyl sulfoxide (DMSO), propylene carbonate (PC), ethylene carbonate (EC), dimethyl carbonate (DMC), γ-butyrolactone (GBL), acetonitrile (AN ), Methoxypropionitrile (MPN), tetrahydrofuran (THF), toluene, methylene chloride, methoxyacetonitrile (MAN), N-methylpyrrolidinone (NMP), 2-methyltetrahydrofuran, 1,3-dioxane, 1,4-dioxane Anisole, monoglyme, propionitrile, 4-methyl-2-pentanone, butyronitrile, valeronitrile, benzonitrile, 1,2-dichloroethane, dimethoxyethane, methyl formate, ethyl acetate, methyl propionate , Ethyl propionate, vinylene carbonate, 1,2-butylene carbonate, methyl ethyl carbonate, dimethylthioformamide, sulfolane, 3-methyl-sulfolane, trimethyl phosphate, triethyl phosphate, nitromethane, acetone, chloroform, dichloromethane and carbon tetrachloride The gelling agent according to claim 8, which is one or more selected from the group consisting of:
The organic solvent is dimethylacetamide (DMA), dimethylformamide (DMF), dimethylsulfoxide (DMSO), propylene carbonate (PC), ethylene carbonate (EC), γ-butyrolactone (GBL), acetonitrile (AN) methoxypropionitrile ( 10 or more selected from the group consisting of MPN), methoxyacetonitrile (MAN), N-methylpyrrolidinone (NMP), acetone, chloroform, dichloromethane and carbon tetrachloride. Gelling agent.
The ionic liquid includes a cation species and an anion species, and the cation may have a substituent, an imidazolium ion, a pyridinium ion, a tetraalkylammonium ion, a pyrrolidinium ion, a piperidinium ion, a tetraalkyl One or more selected from the group consisting of phosnium ion, pyrazolium ion, trialkylsulfonium ion, morpholium ion, and guanidinium ion, and the anion is a halide ion (fluorine, chlorine, Iodine and bromine), tetrafluoroborate ion (BF 4 − ), hexafluorophosphate ion (PF 6 − ), bis (trifluoromethanesulfonyl) imide ion (TFSA − ), thiocyanate ion (SCN − ), nitrate ion ( NO 3 -), sulfuric acid Ions (SO 4 2− ), thiosulfate ions (S 2 O 3 2− ), carbonate ions (CO 3 2− ), hydrogen carbonate ions (HCO 3 − ), phosphate ions, phosphite ions, hypophosphorous acid Acid ions, halogen oxide acid ions (XO 4 − , XO 3 − , XO 2 − and XO − , where X is fluorine, chlorine, bromine or iodine), halogenated acetate ions ((CX n H 3-n ) COO − , where X is fluorine, chlorine, bromine or iodine, n is 1 to 3, and tetraphenylborate ion (BPh 4 − ) and its derivatives (B (Aryl) ) 4 -, wherein it is selected from the group consisting of phenyl group) having Aryl = substituent is one or more gelling agent according to claim 8.
The gel according to claim 8, wherein the electrolyte solution is one or more selected from the group consisting of a solution containing iodine and iodide, a solution containing lithium ions, and a solution containing a tetraalkylammonium salt. Agent.
The gelling agent according to any one of claims 1 to 12, wherein the content of the polymer compound is 15 to 75% by weight based on the gelling agent.
The gelling agent according to any one of claims 1 to 13, wherein the content of the crosslinking agent is 25 to 85% by weight based on the gelling agent.
The gelling agent according to any one of claims 8 to 14, wherein the total content of the liquid medium is 0.1 to 50% by weight in forming the gel.
The gelling agent according to any one of claims 1 to 15, which is used for forming a gel used in a region in contact with an electrode.
A gel formed using the gelling agent according to any one of claims 1 to 16.
A cross-linking agent used for forming the gelling agent according to any one of claims 1 to 16.
A method for producing a gel using the gelling agent according to any one of claims 1 to 16,
The said method including the process of mixing a gelatinizer and a liquid medium.