JPS6029292B2 - organic liquid gel - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an organic liquid gel obtained by adding a specific resin to an organic medium that is liquid at room temperature.

More specifically, gelation is obtained by blending an appropriate amount of a resin obtained by neutralizing a crosslinked anionic polymer substance with a specific higher amine and/or quaternary ammonium salt into an organic medium that is liquid at room temperature. This invention relates to an organic liquid gel useful as a fuel, etc. Conventionally, in order to gel an organic medium such as alcohol in order to obtain gelled fuel, etc.,
A method is known in which a dehydrated condensate of aromatic fulldehyde and polyhydric alcohol with a valence of 5 or more is added as a gelling agent, but the resulting gel generates an extremely large amount of carbon when burned, so it is environmentally friendly. In addition, in order to sufficiently melt the gelling agent, it is necessary to heat the organic medium close to its boiling point, and if left for a long period of time, the formed gel will easily become a replica and will be damaged. It is stable. On the other hand, starch-
A gelling agent in which a queso compound of polyacrylonitrile graft copolymer is neutralized with an amine has been proposed (Japanese Patent Publication No. 54
14157), this gelling agent is useful for organic aqueous fluids containing water, does not contain water, and exhibits little gelling ability for organic solvents. The present inventors have solved the problems with such gels, that is, they do not require high temperatures, form gels quickly, do not require water, and do not fall apart even if left for a long period of time.

As a result of intensive research aimed at providing an organic liquid gel, we found that a gel obtained by adding a specific crosslinked polymer substance and a resin obtained by neutralizing amamine or quaternary ammonium salt to an organic medium. discovered that the drawbacks of conventional gels could be overcome and completed the present invention. That is, the present invention provides a crosslinked polymeric substance having an anionic substituent (carboxylic acid, sulfonic acid) with the general formula 1: [wherein R,,R
2 and R3 are both selected from hydrogen, alkyl, alkylene, phenyl, benzyl, and hydroxyalkyl, and the sum of the carbon numbers contained in R,, R2 and R3 is 6 to 4.
8 Preferably an amine represented by 9 to 36 and/or an amine represented by the general formula RO [wherein R4, R5, R6 and R7 are all hydrogen,
alkyl, alkylene, phenyl, benzyl or hydroxyalkyl, or R4, R5 and R6 are
Together with the nitrogen to which they are attached, they form a pyridinium or picolium ring, R7 is alkyl, alkylene, phenyl, benzyl or hydroxyalkyl, R4
, the total number of carbon atoms contained in R5, R6 and R7 is 8 to
It is 48.

An organic liquid gel is provided by adding a resin neutralized with a quaternary ammonium salt represented by X is a halogen or an acid anion to an organic medium and gelling it. Thus, according to the present invention, a resin obtained by neutralizing a crosslinked polymeric substance having an anionic substituent with an amine and/or quaternary ammonium salt represented by the general formula 1 and/or , 0 for various organic media
．． The content may be 1% by weight or more, preferably 0.3 to 50% by weight, and the hardness of the gel forming body can be freely adjusted by adjusting the amount of the gelling agent added.

The resin used in the present invention can form a gel by simply adding it to an organic solvent, and there is no need to heat it.

Further, the stability after gel formation was extremely excellent, and no change was observed over a period of 3 months in a closed container. Although there is no need to add water for gelling, it has excellent gelling ability even for mixtures of water and organic media. Organic media that can be gelled include alcohols such as methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol, and benzyl alcohol; ketones such as acetone and methyl ethyl ketone; amides such as formamide and dimethylformamide; hexane and heptane. Saturated hydrocarbons such as; aromatic hydrocarbons such as benzene, toluene, xylene, nitrobenzene;

Examples include halogenated hydrocarbons such as roform, carbon tetrachloride, and methylene chloride; ethers such as tetrahydrofuran, dioxane, and diethyl ether; dimethyl sulfoxide, acetonitrile, and the like. Mixtures of two or more of these may also be mentioned as gelatinable organic media. Furthermore, when the gel is used as a fragrance, insect repellent, or insecticide, it is possible to add active ingredients such as fragrance, insecticidal, and bactericidal ingredients. As the carboxyl group-containing crosslinked anionic group-containing polymer substance used in the present invention, for example, a water bath radical polymerization initiator is added in a petroleum-based aliphatic hydrocarbon solvent as disclosed in JP-A No. 53-55260. An aqueous solution of an alkali metal acrylate having a concentration of 4% by weight or more is dispersed and suspended in the presence of a sorbitan fatty acid ester with an HLB of 3 to 6, and this is polymerized in the absence of a crosslinking agent to separate the solvent and water. An acid-type self-crosslinking polyacrylic acid polymer obtained by washing the removed and dried self-crosslinking polyacrylate with acid, or an acrylic acid and acrylamide N-monosubstituted product disclosed in JP-A-54-199188, or an acrylamide N-monosubstituted product disclosed in JP-A-54-199188. Examples include those obtained by heating, dissolving and polymerizing N-disubstituted products.

Other examples include copolymerizing maleic acid with a monomer that is crosslinkable to styrene and their copolymers, or copolymerizing styrene and maleic anhydride and a monomer that is crosslinkable to these copolymers. After copolymerizing with a single plant,
Examples include crosslinked styrene-maleic acid copolymers obtained by hydrolysis. Furthermore, monomers containing carboxyl groups by hydrolysis, such as acrylic acid esters such as methyl acrylate, ethyl acrylate, and propyl acrylate, and polymers of acrylonitrile can also be used in the present invention.

Examples of crosslinked anionic polymeric substances containing sulfonic acid groups include vinylsulfonic acid, allylsulfonic acid, vinyltoluenesulfonic acid, styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, and sulfopropyl (
meth)acrylate (hereinafter the term (meth)acrylic means both acrylic and methacrylic), 2-
Examples include copolymers of sulfonic acid group-containing monomers such as hydroxy-3-(meth)acryloxypropylsulfonic acid and monomers capable of crosslinking to polymers consisting of one or more of these. It will be done.

Furthermore, examples of crosslinked anionic polymer substances containing carboxyl groups and sulfonic acid groups include copolymers of (meth)acrylic acid and 2-acrylamido-2-methylpropanesulfonic acid, and copolymers of (meth)acrylic acid and styrenesulfonic acid. copolymers of (meth)acrylonitrile and 2-acrylamido-2-methylpropanesulfonic acid, hydrolysates of copolymers of (meth)acrylonitrile and 2-acrylamido-2-methylpropanesulfonic acid, etc., and the proportions of carboxyl groups and sulfonic acid groups in these copolymers are particularly It is not limited and can be selected as appropriate. Next, as a method for producing a crosslinked anionic polymer substance, in addition to a method of simultaneously polymerizing the above monomer and a crosslinking agent to obtain a crosslinked polymer all at once, It can also be obtained by a method in which one or more types of compounds are polymerized and then post-modified with a crosslinking agent having two or more functional groups reactive with carboxyl groups or sulfonic acid groups.

The crosslinking agent used here has at least two polymerizable non-conjugated double bonds, such as di- or trivinylbenzene, dipinyl ether, divinyl ketone, N,N-methylenebisacrylamide, polyisocyanate, etc. Examples of crosslinking agents having at least two functional groups that react with carboxyl groups or sulfonic acid groups include epoxy compounds such as ethylene glycol diglycidyl ether, propylene glycol glycidyl ether, and polyethylene glycol glycidyl ether; Examples include haloepoxyalkanes such as epichlorohydrin and Q-methylepichlorohydrin.

The amount of these crosslinking agents added is preferably in the range of 0.0001 to 1 mol % based on the total monomers constituting the copolymer.

Further, if desired, a water-soluble monomer copolymerizable with the carboxyl group-containing monomer and the sulfonic acid group-containing monomer may be added in an amount of 50 mol% or less based on the total monomers.

Examples of copolymerizable water-soluble monomers include monoethylene unsaturated alcohols such as (meth)allyl alcohol: polyols such as alkylene glycols, polyoxyalkylene glycols, monoethylene unsaturated esters such as hydroxyethyl (meth)acrylate, Hydroxyl group-containing monomers such as hydroxypropyl (meth)acrylate and triethylene glycol (meth)acrylate: (meth)acrylamide; N-alkyl (meth)acrylamide such as N-methylacrylamide, N-
Hexylacrylamide; N,N-dialkyl (meth)
Acrylamides such as N,N-dimethylacrylamide, N,N-di-n- or i-propylacrylamide; N-hydroxyalkyl (meth)acrylamides such as N-methylacrylamide. (meth)acrylamide, N-hydroxyethyl (meth)acrylamide; N,N-dihydroxyalkyl (meth)acrylamide such as N,
Examples include amide group-containing monomers such as N-dihydroxyethyl (meth)acrylamide; vinyl lactams (N-vinylpyrrolidone, etc.). The use of polymeric substances obtained by copolymerizing these water-soluble monomers has the effect of further increasing the gelling ability, particularly when gelling an aqueous organic liquid. In addition to these water-soluble monomers, copolymerizable monomers may be added to the extent that the gelling properties are not deteriorated.

For example, styrene, ethylene, butadiene, propylene, vinylidene chloride, acrylonitrile, vinyl acetate,
Examples include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. When these monomers are added and copolymerized and the resulting polymer material is used,
In particular, the gelling ability for water-insoluble organic solvents is improved.

Further, examples of amines represented by general formula 1 include dipropylamine, dibutylamine, triethylamine, hexylamine, diallylamine, triallylamine,
-diethylaminopropanol, triethanolamine, trioctylamine, N-methylpiverizinebenzylamine, dibenzylamine, phenylcyclohexylamine, and the like.

On the other hand, examples of quaternary ammonium salts represented by general formula D include N-benzylpyridinium chloride, N-
Examples include hydroxyethylpyridinium chloride, tetrabutylammonium sulfate, trioctylmethylammonium chloride, benzyltrimethylammonium chloride, and N-lauryl-4-picolium chloride.

Neutralization of a crosslinked anionic polymer substance and an amine or quaternary ammonium salt represented by general formulas 1 and/or m can be carried out in water, an organic medium, or a water-organic medium. The degree of neutralization with the quaternary ammonium salt is in the range of 0.01 to 1.0.

The resin thus obtained quickly swells in an organic liquid to form a gel.

To obtain a gel of an organic liquid, the resin can simply be dispersed in the organic liquid and soaked for 10 to 60 minutes, without the need for heating or adding any other additives. The amount added in this case can be appropriately selected depending on the purpose of use, but is generally preferably 0.1 to 50% based on the organic liquid.
The gel tends to become harder as the amount added increases. Therefore, according to the present invention, a high-quality organic liquid gel can be obtained quickly at room temperature, and since there is no acid release, it can be stored for a long period of time. It can be used in fields such as fungicides, herbicides, and fumigants.

Furthermore, when the gel forming product of the present invention is conveniently used as fuel, the amount of the gelling agent added is small, and the gelling agent itself is combustible, so the influence of the gelling agent on combustion is small. .

There was no occurrence of force-bonding at all, and there were no problems from an environmental or hygienic standpoint. Hereinafter, the present invention will be explained in more detail with reference to Reference Examples and Examples, but the present invention is not limited by these descriptions.

Reference example 1 400 ml of water, 100 ml of acrylic acid and 0.1 ml of diethylene glycol diacrylate were added to Aya Azusa, nitrogen blowing pipe,
The mixture was charged into a reaction vessel equipped with a thermometer, incubated at 30°C for 3 minutes under a nitrogen stream, and 0.05% of 30% hydrogen peroxide solution and 0.005% of L-ascorbic acid were added as polymerization catalysts. When the mixture was heated in a pot for 8 hours to polymerize, a white crosslinked polymer substance A was obtained.

Reference Example 2 52 tons of styrene, 49 tons of maleic anhydride, 0.05 tons of divinylbenzene, and 400 tons of benzene were charged into a reaction vessel equipped with a gas rod, a nitrogen blowing tube, and a thermometer, and heated under a nitrogen stream. Adding 0.25 ml of 2,2-azobis(2,4-dimethylvaleronitrile) as a polymerization catalyst, the mixture was reacted at 50°C for 3 hours and at 70°C for 3 hours, and after drying in an oven, 200% water was added. Add evening to 100, 0 to 1
Hydrolysis was carried out for 0 hours, washed with acetone and then with ether, and dried at 25q0 to obtain a crosslinked styrene-maleic acid copolymer B.

Reference Example 3 Polymerization was carried out in the same manner as in Reference Example 1 using 100 μm of 2-acrylamido-2-methylpropane sulfonic acid (AMmS, manufactured by Nitto Chemical Co., Ltd.) and 0.5 μm of diethylene glycol diacrylate to obtain a white cross-linked sulfone. An acid group-containing anionic polymer substance C was obtained.

Reference Example 4 400 ml of water, 75 ml of acrylic acid, 25 ml of 2-acrylamide-2-methylpropanesulfonic acid and 0.05 ml of N,N-bismethylol acrylamide were prepared using a chick rod, nitrogen blowing tube, and thermometer. Prepare the reaction vessel,
Lighting was carried out for 30 minutes at 3,000 ℃ under a nitrogen stream, and potassium persulfate was used as a polymerization catalyst at 0.08 liters and sodium hydrogen sulfite was added at 0.08 liters.
After adding 0.3 liters of water, polymerization was carried out at 3,000 ℃ for 5 hours to obtain a white crosslinked copolymer material D.

Reference Example 5 In Reference Example 4, acrylamide was used instead of 2-acrylamide-2-methylpropanesulfonic acid to carry out polymerization, and a white crosslinked copolymer material E was obtained.

Example 1 The crosslinked anionic polymer substance A obtained in Reference Example 1 was
In the evening, the mixture was dispersed in 25 liters of water and neutralized with dibutylamine to give a degree of neutralization of 0.85, then poured onto a tray and dried in vacuo at 60°C.

When this was crushed into powder and dispersed in 10 methanol, after 20 minutes, a gel-like meth/
The rules were obtained. When this gel was burned, no carbon was generated and almost no combustible residue remained. Example 2 The powder obtained in Example 1 was taken overnight and dispersed in 50 ml of ethylene glycol. After 30 minutes, gel-like ethylene glycol was obtained.

Even after this gel was left at room temperature for 3 months, no change was observed in its appearance. Example 3 The anionic polymer substance B5 obtained according to Reference Example 2 was dispersed in 25 days of water and neutralized with trioctylamine,
After adjusting the degree of neutralization to 0.3, it was dried in vacuum at 6000°C.

Then, when this was ground into powder and dispersed in 50 m' of acetone, gel-like acetone was obtained after 30 minutes. Place this in an airtight container and let it stand at room temperature for 3
After leaving it for several months, we observed its appearance and found that there was no chlorine acid and no other changes were observed. Example 4 The anionic polymer substance B5 obtained in Reference Example 2 was dispersed in 250 mg of acetone, neutralized with dibenzylamine to a degree of neutralization of 0.3, poured onto a tray, and vacuumed. 4th year middle school
Dry at 0oo.

One day of this powder was dispersed in 50 days of a mixed solvent of acetone:benzene in a ratio of 1:1, and an acetone-benzene mixed solvent that gelled after 1 hour was obtained. This gel remained stable even after being left in a closed container for 3 months. Example 5 Crosslinked anionic polymer substance C obtained according to Reference Example 3
The IO solution was dispersed in 50 ml of acetone, neutralized with diallylamine to a degree of neutralization of 0.3, and then dried in vacuo at 40 qo.

Then, when this was ground into a powder and dispersed in a mixed solvent with an acetonitrile:methanol ratio of 3:1, an acetonitrile/methanol mixture gelled after 2 minutes. was gotten. This gel was stable for 3 months. Example 6 The anionic polymer substance D5 obtained in Reference Example 4 was dispersed in water for 25 minutes, neutralized with trietanolamin to a degree of neutralization of 0.8, and then poured onto a tray. in vacuum 6
Dry at 0oC.

Grind this into powder and mix it with 95% methanol and 2 parts.
When the gel was dispersed in 0000, a 95% methanol gel with very high hardness was obtained. Example 7 The anionic polymer substance D5 obtained in Reference Example 4 was dispersed in 25-mL water, neutralized with tetrabutylammonium sulfate to a degree of neutralization of 0.3, and then poured onto a tray. , dried in vacuo at 60 CO.

When this powder was ground and dispersed in 100 days of dimethyl sulfoxide, a gel of dimethyl sulfoxide was obtained. This gel is stable for more than 3 months,
No change was observed in appearance. Example 8 The anionic polymer substance E5 obtained in Reference Example 5 was
After dispersing it in acetone and neutralizing it with 2-ethylhexylamine to a degree of neutralization of 0.7, it was dispersed in a vacuum at 40°C.
It was dried at 00.

Claims (1)

[Claims] 1. An anionic polymeric substance containing a crosslinked carboxyl group and/or sulfonic acid group is defined by the general formula I: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1, R_2 and R_3 are Also hydrogen,
Alkyl, alkylene, phenyl, benzyl or hydroxyalkyl, and the total number of carbon atoms contained in R_1, R_2 and R_3 is 6 to 36] and/or general formula II ▲Mathematical formula, chemical formula, table, etc. ▼ [In the formula, R_4, R_5, R_6 and R_7 are all hydrogen, alkyl, alkylene, phenyl, benzyl or hydroxyalkyl, or R_4, R_5 and R_6 together with the nitrogen to which they are bonded represent a pyridinium ring or a picolium ring. , R_7 is alkyl,
It is alkylene, phenyl, benzyl or hydroxyalkyl, and the total number of carbon atoms contained in R_4, R_5, R_6 and R_7 is 8 to 48. An organic liquid gel obtained by adding a resin obtained by neutralizing with a quaternary ammonium salt represented by X is a halogen or an acid anion to an organic medium that is liquid at room temperature.