JP2022151757A - Emulsifier composition for reverse-phase emulsion polymerization and method for producing polymer flocculant - Google Patents

Abstract

To provide an emulsifier composition that can achieve both of reverse-phase emulsification and phase inversion without increasing the amount of use of an emulsifier.SOLUTION: An emulsifier composition for reverse-phase emulsion polymerization contains a compound in which three or more molecules of C12-22 aliphatic carboxylic acids form ester bonds with one molecule of an alkylene oxide-added polyol having a valence of three or more, the compound having an HLB value of 5-12. The alkylene oxide-added polyol having a valence of three or more should be preferably an alkylene oxide-added polyhydric alcohol having a valence of four or more.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to an emulsifier composition for inverse emulsion polymerization and a method for producing a polymer flocculant.

As a method for producing a polymer flocculant, a reversed-phase suspension polymerization method (see, for example, Patent Document 1), a reversed-phase emulsion polymerization method, and the like are known. Among these methods, the inverse emulsion polymerization method has the advantage of being able to produce a high-molecular-weight water-affinitive polymer as a low-viscosity solid content.
In a general inverse emulsion polymerization method, a water-in-oil emulsion is formed by adding an oil phase containing an emulsifier, a hydrophobic dispersion medium, etc. to an aqueous phase containing a polymerizable monomer, water, and optionally a cross-linking agent. a step of polymerizing a polymerizable monomer using a polymerization initiator in the water-in-oil emulsion to form a polymer emulsion; and a step of adding a phase change agent to the polymer emulsion.

JP 2014-64988 A

The emulsifier used in the reverse phase emulsion polymerization method provides stability to the polymer emulsion obtained after polymerization by enabling emulsification of the polymerizable monomer into the oil phase in the step prior to polymerization of the polymerizable monomer. In the polymerization process, it provides stability to the polymer emulsion by suppressing sedimentation resistance, viscosity change over time and premature reversal.
In general inverse emulsion polymerization, an emulsifier with a low HLB value (e.g., an emulsifier with an HLB value of 2 to 7, "a low HLB However, when a low HLB emulsifier is used, the phase inversion is poor, so it may be necessary to add a large amount of the phase inversion agent. Increasing the proportion of phase change agent (usually a highly hydrophilic surfactant) can reduce the stability of the polymer emulsion or increase the viscosity unacceptably.
On the other hand, conventional emulsifiers with a high HLB value (for example, emulsifiers with an HLB value of 8 or more, also called "high HLB emulsifiers") have inferior reverse phase emulsifying properties than low HLB emulsifiers. Alternatively, it may be necessary to use a low HLB emulsifier. If the total amount of emulsifiers used increases, such as by increasing the amount of high-HLB emulsifiers or combining high-HLB emulsifiers and low-HLB emulsifiers, the purity of the polymer flocculant will decrease, which may lead to quality deterioration. , there are also concerns about the environmental impact.
An object of the present invention is to provide an emulsifier composition capable of achieving both reverse phase emulsification and phase inversion without increasing the amount of emulsifier used, and a method for producing a polymer flocculant using the emulsifier composition. .

The present inventors arrived at the present invention as a result of intensive studies in order to solve the above problems.
That is, the present invention includes a compound in which 3 or more molecules of an aliphatic carboxylic acid having 12 to 22 carbon atoms are ester-bonded to 1 molecule of an alkylene oxide adduct of a trivalent or higher polyol, and the HLB value of the compound is 5 to 5. 12, and a method for producing a polymer flocculant for producing a polymer flocculant by a reverse phase emulsion polymerization method using the emulsifier composition.

INDUSTRIAL APPLICABILITY According to the present invention, there is provided an emulsifier composition for inverse emulsion polymerization capable of achieving both inverse emulsifiability and phase inversion without increasing the amount of emulsifier used, and a method for producing a polymer flocculant using the emulsifier composition. can provide

[Emulsifier composition]
The emulsifier composition of the present invention contains a compound in which three or more molecules of an aliphatic carboxylic acid having 12 to 22 carbon atoms are ester-bonded to one molecule of an alkylene oxide adduct of a trihydric or higher polyol. Said compound is a compound that functions as an emulsifier.
In the following, "a compound in which three or more molecules of an aliphatic carboxylic acid having 12 to 22 carbon atoms are bonded to one molecule of an alkylene oxide adduct of a trihydric or higher polyol" is referred to as "compound (A)" or "(A) It is sometimes called an ingredient. Compound (A) may be used alone or in combination of two or more.

An alkylene oxide adduct (a1 ) include alkylene oxide adducts of trihydric or higher aliphatic polyhydric alcohols (a1-1), alkylene oxide adducts of sugars (a1-2), and the like.

In the alkylene oxide adduct (a1-1) of a trihydric or higher aliphatic polyhydric alcohol, the trihydric or higher aliphatic polyhydric alcohol includes an alkane polyol having 3 to 36 carbon atoms and an intramolecular or intermolecular dehydrate thereof. etc. Specific examples of trihydric or higher aliphatic polyhydric alcohols include glycerin, trimethylolethane, trimethylolpropane, erythritol, diglycerin, pentaerythritol, sorbitol, sorbitan, polyglycerin and dipentaerythritol. As these aliphatic polyhydric alcohols, trihydric to heptahydric polyhydric alcohols are preferable, and tetrahydric to hexahydric polyhydric alcohols are more preferable.

The alkylene oxide (hereinafter also referred to as "AO") in the alkylene oxide adduct (a1-1) of a trihydric or higher aliphatic polyhydric alcohol includes AO having 2 to 4 carbon atoms [ethylene oxide (EO), 1, 2- or 1,3-propylene oxide (PO) and 1,2-, 1,3-, 1,4- or 2,3-butylene oxide (BO), etc.]. AO may be used alone or in combination of two or more. AO preferably has 2 to 3 carbon atoms, more preferably contains EO, and further preferably contains EO and PO.

The number of moles of AO to be added to 1 mole of a trihydric or higher aliphatic polyhydric alcohol is preferably 5 to 45 moles, more preferably 10 to 40 moles. If the number of AO addition moles is too small, the HLB value becomes too small, which may adversely affect the phase inversion. However, if it is within the above preferred range, it is possible to achieve both phase inversion and reversed phase emulsification properties without being affected by such effects.

Sugars in the alkylene oxide adduct of sugars (a1-2) include, for example, glucose, fructose, sucrose, and methylglucoside.
Examples of AO in the alkylene oxide adduct of sugar (a1-2) are the same as those described in (a1-1) above. The preferred AO and the preferred range of the number of added moles are the same as in (a1-1) above.

Examples of the alkylene oxide adduct (a1) of a trivalent or higher polyol include an alkylene oxide adduct of a polyol having 3 to 6 carbon atoms and a compound obtained by adding an alkylene oxide having 2 to 4 carbon atoms to a trivalent or higher polyol. preferable. Further, the alkylene oxide adduct (a1) of a trihydric or higher polyol is preferably an alkylene oxide adduct (a1-1) of a trihydric or higher aliphatic polyhydric alcohol, and an alkylene oxide of a tetrahydric or higher polyhydric alcohol. Adducts are more preferred, and AO adducts of sorbitol and AO adducts of sorbitan are even more preferred.

As the aliphatic carboxylic acid (a2) in the compound (A) in which three or more molecules of an aliphatic carboxylic acid having 12 to 22 carbon atoms are bonded to one molecule of an alkylene oxide adduct of a trivalent or higher polyol, for example, the number of carbon atoms Aliphatic monocarboxylic acids of 12 to 22 (including the carbon in the carbonyl group) can be mentioned.
Examples of aliphatic monocarboxylic acids having 12 to 22 carbon atoms include dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), pentadecanoic acid, hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), isostearic acid, and oleic acid. , linoleic acid, eicosanoic acid (arachidic acid), and docosanoic acid (behenic acid).

The aliphatic carboxylic acid (a2) is preferably an aliphatic monocarboxylic acid having 16 to 22 carbon atoms (including the carbon of the carbonyl group), more preferably an aliphatic monocarboxylic acid having 16 to 18 carbon atoms, and 16 to 18 carbon atoms. 18-unsaturated aliphatic monocarboxylic acids are more preferred, with oleic acid and linoleic acid being particularly preferred.

In the compound (A), one molecule of an alkylene oxide adduct of a tetrahydric or higher polyhydric alcohol and 3 or more molecules of an aliphatic carboxylic acid having 16 to 22 carbon atoms are used from the viewpoint of achieving both reverse phase emulsification and phase inversion. It is preferably an ester formed by bonding.

In the compound (A), three or more molecules of the aliphatic carboxylic acid bonded to one molecule of the alkylene oxide adduct of a trivalent or higher polyol may be the same (one type), or two or more types. may be a combination of It is preferable that three or more molecules of the aliphatic carboxylic acid bonded to one molecule of the alkylene oxide adduct of trivalent or higher polyol are the same (one type).

The compound (A) includes a structure in which an aliphatic carboxylic acid is ester-bonded to a (poly)alkyleneoxy group bonded to each of three or more hydroxyl groups of a trivalent or higher polyol. In the structure, the trivalent or higher polyol corresponds to the trivalent or higher polyol constituting the alkylene oxide adduct of the trivalent or higher polyol, and the (poly)alkyleneoxy group is the alkylene oxide addition of the trivalent or higher polyol. The aliphatic carboxylic acid corresponds to the aliphatic carboxylic acid having 12 to 22 carbon atoms that constitutes the compound (A). A (poly)alkyleneoxy group means an alkyleneoxy group (one alkyleneoxy group) and/or a polyalkyleneoxy group (two or more alkyleneoxy groups). In the above structure, the number of alkyleneoxy groups per hydroxyl group possessed by the trihydric or higher polyol is preferably 1.5 to 15, and 1.5 to 10 is more preferred, and 2.5 to 10 is even more preferred.

Preferable compounds as the compound (A) are trioleate (polyoxyethylene sorbitol trioleate) of EO 10 to 40 mol adduct of sorbitol, and triolein of EO/PO (total 10 to 40 mol) adduct of sorbitol. acid ester (polyoxyethylene polyoxypropylene sorbitol trioleate), tetraoleate (polyoxyethylene sorbitol tetraoleate) adduct of EO 10-40 moles of sorbitol, EO/PO of sorbitol (total 10-45 mol) adduct tetraoleate (polyoxyethylene polyoxypropylene sorbitol tetraoleate), EO of sorbitol 10-40 mol adduct hexaoleate (polyoxyethylene sorbitol hexaoleate) and EO of sorbitol - Polyoxyethylene polyoxypropylene sorbitol hexaoleate ester of adduct of PO (10 to 40 mol in total) and the like. One type of these may be used, or two or more types may be combined. In the present specification, for example, "trioleic acid ester of EO 10 mol adduct of sorbitol" means an ester formed by bonding 3 molecules of oleic acid (aliphatic carboxylic acid) to 1 molecule of EO 10 mol adduct of sorbitol. do.

In the present invention, the compound (A) has an HLB (Hydrophile-Lipophile Balance) value of 5-12. When the compound (A) has an HLB value of 5 to 12, both inverse emulsifiability and phase inversion can be achieved without increasing the amount of emulsifier used. If the HLB value of the compound (A) is less than 5, the phase inversion will be insufficient, and if the HLB value exceeds 12, the reverse phase emulsifying property will be insufficient. The HLB value of compound (A) is preferably 5.5 to 11.5.

In the present invention, the HLB value represents the balance between hydrophilicity and lipophilicity, and is obtained from the following formula (1) ("Synthesis of Surfactants and Their Applications", page 501, published by Maki Shoten in 1957; Introduction to Surfactants", pp. 212-213, published by Sanyo Kasei Kogyo, 2007, etc.).
HLB value = 10 x (inorganic/organic) (1)
In formula (1), the parenthesis indicates the ratio of the inorganic and organic properties of the organic compound, and the ratio can be calculated from the values described in the above literature.

The compound (A) is an alkylene oxide adduct of a trivalent or higher polyol (a compound in which three or more hydroxyl groups of a trivalent or higher polyol are respectively bonded to (poly)alkyleneoxy groups), and an aliphatic carboxylic acid. It can be produced by performing an esterification reaction using
Examples of the alkylene oxide adduct of a trivalent or higher polyol used in the method for producing the compound (A) include the same compounds as the alkylene oxide adduct of a trivalent or higher polyol (a1) described above, which are preferable. is the same.
Examples of the aliphatic carboxylic acid used in the method for producing compound (A) include the same compounds as those described for the above-described aliphatic carboxylic acid (a2), and the preferred ones are also the same.

The emulsifier composition may contain an emulsifier other than compound (A) [referred to as compound (B)] in addition to compound (A).
Examples of the compound (B) include an alkylene oxide adduct (B1) of a higher alcohol (having 10 to 30 carbon atoms), and a compound (B2 ) and a compound (B3) in which one molecule or two molecules of an aliphatic carboxylic acid are bound to one molecule of an alkylene oxide adduct of a trivalent or higher polyol. In the following, "a compound (B2) in which one molecule or two molecules of an aliphatic carboxylic acid are bonded to a trivalent or higher polyol" is referred to as a compound (B2), and "one molecule of an alkylene oxide adduct of a trivalent or higher polyol and an aliphatic A compound (B3) in which one or two molecules of a group carboxylic acid are bonded together is also referred to as a "compound (B3)."

Higher alcohols in the higher alcohol AO adduct (B1) include decyl alcohol, dodecyl alcohol, pentadecyl alcohol, hexadecyl alcohol, octadecylalconol (stearyl alcohol), cis-9-octadecen-1-ol (oleyl alcohol ), icosyl alcohol and docosanol (behenyl alcohol).
Examples of AO in the AO adduct of higher alcohol (B1) are the same as those described in (a1-1) above, and the number of moles of AO added is 1 to 20 per 1 mol of the higher alcohol. Preferably.
As the higher alcohol AO adduct (B1), an oleyl alcohol AO adduct is preferable.

In the compound (B2) in which one or two molecules of an aliphatic carboxylic acid are bonded to a trihydric or higher polyol, examples of the trihydric or higher polyol include trihydric or higher aliphatic polyhydric alcohols and saccharides. Examples of the aliphatic polyhydric alcohol having a valence of 3 or more include those similar to the aliphatic polyhydric alcohol having a valence of 3 or more in the alkylene oxide adduct (a1-1) of the aliphatic polyhydric alcohol having a valence of 3 or more. Examples of the saccharides include the same saccharides as the alkylene oxide adducts (a1-2) of the above saccharides.

Examples of the aliphatic carboxylic acid for the compound (B2) include those similar to the aliphatic carboxylic acid (a2) for the compound (A).

As the compound (B2), sorbitan monooleate and glycerol monooleate (glycerol monooleate) are preferable.

As the alkylene oxide adduct of a trivalent or higher polyol in the compound (B3) in which one molecule or two molecules of an aliphatic carboxylic acid is bonded to one molecule of the alkylene oxide adduct of a trivalent or higher polyol, Examples include an alkylene oxide adduct of an aliphatic polyhydric alcohol (b3-1) and an alkylene oxide adduct of a sugar (b3-2).

As the trihydric or higher aliphatic polyhydric alcohol in the alkylene oxide adduct of a trihydric or higher aliphatic polyhydric alcohol (b3-1), the alkylene oxide adduct of the trihydric or higher aliphatic polyhydric alcohol (a1- The same as the aliphatic polyhydric alcohol having a valence of 3 or more in 1) can be mentioned.
In the alkylene oxide adduct (b3-1) of a trihydric or higher aliphatic polyhydric alcohol, the same AO as described in (a1-1) above can be mentioned, and the number of moles of AO added is It is preferably 5 to 40 mol per 1 mol of group polyhydric alcohol.

Examples of the sugar in the alkylene oxide adduct of sugar (b3-2) include the same sugars as in the alkylene oxide adduct of sugar (a1-2). Examples of AO in the alkylene oxide adduct of sugar (b3-2) are the same as those described in (a1-1) above.

Examples of the aliphatic carboxylic acid for the compound (B3) include those similar to the aliphatic carboxylic acid (a2) for the compound (A).

As the compound (B3), a monooleic acid ester of an EO adduct of sorbitan (the number of EO adducts is 1 to 30 mol) is preferable.

As the compound (B), the compound (B2) and the compound (B3) are preferable. 30 mol) is more preferred. One type of these may be used, or two or more types may be combined.

It is said that the content of compound (A) in the emulsifier composition can achieve both reverse phase emulsification and phase inversion when producing a polymer flocculant by a reverse phase emulsion polymerization method using the composition. From a viewpoint, it is preferably 10% to 100% by weight, more preferably 20% to 100% by weight, based on the weight of the emulsifier composition.

The content of compound (B) in the emulsifier composition is preferably 0% to 90% by weight, more preferably 0% to 80% by weight, based on the weight of the emulsifier composition.

The HLB value of the emulsifier composition of the present invention is not particularly limited. The HLB value of the emulsifier composition is preferably 6 to 12, more preferably 7 to 12, from the viewpoint of achieving both reverse phase emulsification and phase inversion when producing a polymer flocculant.

The HLB value of the emulsifier composition can be adjusted by adjusting the types and blending amounts of the emulsifiers (compound (A), compound (B), etc.) used. When the emulsifier composition is prepared using two or more emulsifiers, the HLB value of the emulsifier composition can be calculated by weighted average. For example, the HLB value of an emulsifier composition containing M1 parts by weight of a compound (A) with an HLB value of h1 and M2 parts by weight of a compound (B) with an HLB value of h2 as an emulsifier can be calculated by the following formula.
HLB value of emulsifier composition = (h1 x M1 + h2 x M2) / (M1 + M2)

The emulsifier composition of the present invention easily forms a water-in-oil emulsion (excellent in reverse phase emulsifying property) and has good compatibility with reverse phase inversion. It has the effect of being compatible with phase inversion. Therefore, it is useful as an emulsifier in the step of forming a water-in-oil emulsion when producing a polymer flocculant by inverse emulsion polymerization.

[Method for producing polymer flocculant]
The method for producing a polymer flocculant of the present invention is a method of producing a polymer flocculant by reverse phase emulsion polymerization using the emulsifier composition of the present invention.

As a method for producing the polymer flocculant of the present invention, for example, water-in-oil by adding an oil phase containing the emulsifier composition of the present invention and a hydrophobic dispersion medium to an aqueous phase containing a polymerizable monomer and water. A step of forming a type emulsion (step 1), a step of polymerizing a polymerizable monomer using a polymerization initiator in the water-in-oil emulsion to form a polymer emulsion (step 2), and adding a phase change agent to the polymer emulsion. A method including the step of adding (step 3) can be mentioned. The manufacturing method will be described below.

[Step 1]
Step 1 is a step of forming a water-in-oil emulsion by adding an oil phase containing an emulsifier composition, a hydrophobic dispersion medium and the like to an aqueous phase containing a polymerizable monomer, water and the like.

(aqueous phase)
Examples of polymerizable monomers contained in the aqueous phase include water-soluble cationic monomers (w1), water-soluble anionic monomers (w2) and water-soluble nonionic monomers (w3). These monomers may be used alone or in combination of two or more.
Here, water-soluble means that the solubility in water is 1 g or more/100 g of water (20° C.).

Examples of the water-soluble cationic monomer (w1) include a nitrogen atom-containing (meth)acrylate salt (w11) and a nitrogen atom-containing (meth)acrylamide salt (w12). As used herein, "(meth)acrylate" means acrylate and/or methacrylate, and "(meth)acrylamide" means acrylamide and/or methacrylamide.

Examples of the nitrogen atom-containing (meth)acrylate in the nitrogen atom-containing (meth)acrylate salt (w11) include nitrogen atom-containing (meth)acrylates having 5 to 8 carbon atoms. Specific examples of nitrogen atom-containing (meth)acrylates having 5 to 8 carbon atoms include aminomethyl (meth)acrylate, aminoethyl (meth)acrylate, aminopropyl methacrylate, aminobutyl (meth)acrylate and dimethylaminoethyl acrylate. is given.
Salts of nitrogen atom-containing (meth)acrylate salts (w11) include salts of inorganic acids (hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, etc.), organic acids (methanesulfonic acid, carboxylic acid, phosphonic acid, methyl chloride, etc.) salt, etc.

Examples of the nitrogen atom-containing meta(meth)acrylamide in the nitrogen atom-containing (meth)acrylamide salt (w12) include nitrogen atom-containing meta(meth)acrylamides having 5 to 8 carbon atoms. Specific examples of nitrogen atom-containing meta(meth)acrylamides having 5 to 8 carbon atoms include aminomethyl(meth)acrylamide, aminoethyl(meth)acrylamide, aminopropyl(meth)acrylamide, and aminobutyl(meth)acrylamide. can give.
Examples of the nitrogen atom-containing (meth)acrylamide salt (w12) include the same salts as the nitrogen atom-containing (meth)acrylate salt (w11).

Of the water-soluble cationic monomers (w1), from the viewpoint of aggregation performance and copolymerizability, preferred are nitrogen atom-containing (meth)acrylate salts (w11), and more preferred are aminoethyl (meth)acrylate salts. and salts of aminopropyl (meth)acrylate, particularly preferred are salts of aminoethyl (meth)acrylate. Furthermore, hydrochlorides, sulfates and methanesulfonates are preferred among these salts.

Examples of the water-soluble anionic monomer (w2) include acrylic acid, methacrylic acid, vinylsulfonic acid, vinylbenzenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, salts thereof (alkali metal salts) and mixtures thereof. be done.
Among these, acrylic acid, methacrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, and salts thereof are preferable, more preferably acrylic acid, 2 - acrylamido-2-methylpropanesulfonic acid, and salts thereof.

Water-soluble nonionic monomers (w3) include (meth)acrylamide, N-alkyl (C1-3) (meth)acrylamide [N-methyl and isopropyl (meth)acrylamide, etc.]. Among these, acrylamide and N-methylacrylamide are preferred from the viewpoint of flocculating performance and polymerizability of the polymer flocculant, and acrylamide is more preferred.

The polymerizable monomer may contain a water-soluble unsaturated monomer (w4) other than the water-soluble cationic monomer (w1), water-soluble anionic monomer (w2) and water-soluble nonionic monomer (w3). Other water-soluble unsaturated monomers (w4) include, for example, water-soluble unsaturated monomers described in JP-A-2018-130652 (excluding the above (w1) to (w3)).
In addition to the water-soluble unsaturated monomers (w1) to (w4), the polymerizable monomer may contain a water-insoluble unsaturated monomer. Examples of such water-insoluble unsaturated monomers include water-insoluble unsaturated monomers described in JP-A-2018-130652.

Polymerizable monomers may include, for example, the following crosslinkable monomers. A crosslinkable monomer means a monomer having a total of 2 or more (preferably 2 to 8) polymerizable unsaturated groups and/or reactive epoxy groups. Examples of such crosslinkable monomers include N,N-methylenebis(meth)acrylamide [methylenebis(meth)acrylamide] and crosslinkable monomers described in JP-A-2014-64988. Methylenebisacrylamide is preferred as the crosslinkable monomer.

The polymerizable monomer concentration (% by weight) in the monomer solution (aqueous phase) is preferably 30% to 90% by weight, more preferably 40% to 85% by weight. The concentration of the polymerizable monomer can be appropriately adjusted depending on the composition (kind) of the polymerizable monomer and the kind of the polymerization initiator described below.

(oil phase)
The oil phase contains a hydrophobic dispersion medium along with the emulsifier composition of the present invention. A hydrophobic dispersion medium means a dispersion medium having a solubility in water (20° C.) of less than 1 g/100 g of water.

Hydrophobic dispersion media include hydrocarbons {linear aliphatic hydrocarbons having 5 to 12 carbon atoms [such as n-hexane, n-heptane, n-octane, n-nonane and n-decane], branched aliphatic group hydrocarbons [e.g. isoparaffin (e.g. "ISOSOL 400" manufactured by ENEOS Corporation), alicyclic-containing hydrocarbons having 5 to 12 carbon atoms [e.g. cyclopentane, cyclohexane, cycloheptane, methylcyclohexane, cyclooctane, decalin, etc. ], and aromatic ring-containing hydrocarbons having 6 to 12 carbon atoms [e.g., benzene, toluene, xylene and ethylbenzene]}, ketones {aliphatic ketones having 3 to 10 carbon atoms [e.g., methyl-n-propyl ketone, diethyl ketone and methyl isobutyl ketone, etc.], alicyclic-containing ketones having 5 to 10 carbon atoms [e.g., cyclopentanone and cyclohexanone, etc.] and aromatic ring-containing ketones having 8 to 13 carbon atoms, [e.g., acetophenone, benzophenone, etc.], etc.}, ethers {carbon Aliphatic ethers having 4 to 8 carbon atoms [eg di-n-propyl ether, di-n-butyl ether and diethylene glycol dimethyl ether], cyclic ethers having 4 to 18 carbon atoms [eg tetrahydropyran etc.] and aromatics having 7 to 12 carbon atoms ring-containing ether [e.g. anisole etc.] etc.}, ester {aliphatic ester having 3 to 10 carbon atoms [e.g. n-butyl acetate and isobutyl acetate etc.], alicyclic ester containing 7 to 12 carbon atoms [e.g. cyclohexyl acetate and cyclohexane methyl carboxylate, etc.] and aromatic ring-containing esters having 8 to 13 carbon atoms [e.g., methyl benzoate, ethyl benzoate, n-butyl benzoate, benzyl acetate, dimethyl phthalate, diethyl phthalate, di-n-butyl phthalate, etc.], etc. } is mentioned.
Of these, from the viewpoint of handling during production, preferred are aliphatic hydrocarbons, alicyclic-containing hydrocarbons, aliphatic esters and alicyclic-containing esters, and more preferred are n-hexane, n-heptane, n-octane, n-nonane, n-decane, cyclohexane, methylcyclohexane, n-butyl acetate, isobutyl acetate, isoparaffin and cyclohexyl acetate.

(water-in-oil emulsion)
A water-in-oil emulsion is formed by adding a hydrophobic dispersion medium and an oil phase containing the emulsifier composition of the present invention to an aqueous phase containing a polymerizable monomer, water, and the like, and mixing if necessary. The method of adding the oil phase to the aqueous phase may be batch addition or dropwise addition. The method and conditions for mixing the water phase and the oil phase can be set in consideration of the components contained in the water phase and the components contained in the oil phase.

The amount of the hydrophobic dispersion medium used is preferably 20 parts by weight or more based on 100 parts by weight of the total weight of the monomer solution (aqueous phase) from the viewpoint of the stability of the emulsion (both emulsions before and after polymerization). More preferably 25 parts by weight or more, preferably 1000 parts by weight or less, more preferably 400 parts by weight or less, still more preferably 100 parts by weight or less from the viewpoint of productivity.

The lower limit of the amount of the compound (A) used is preferably 3 parts by weight or more, more preferably 5 parts by weight, with respect to 100 parts by weight of the hydrophobic dispersion medium, from the viewpoint of achieving both reverse phase emulsification and phase inversion. That's it. The upper limit of the amount of the compound (A) used is preferably 20 parts by weight or less, more preferably 15 parts by weight or less. When an emulsifier composition containing compound (A) is used, a smaller amount than when a conventional high HLB (HLB value is 8 or more) emulsifier is used, and the characteristics of both reverse phase emulsification and phase inversion are exhibited. Therefore, it is possible to suppress deterioration in quality caused by an increase in the proportion of the emulsifier component in the polymer flocculant.

(Step 2)
Step 2 is a step of using a polymerization initiator in the water-in-oil emulsion to polymerize the polymerizable monomers to form a polymer emulsion. By performing step 2, a polymer emulsion containing a polymer obtained by polymerizing a polymerizable monomer is obtained. The polymer contained in the polymer emulsion is a polymer that functions as a polymer flocculant.

Examples of polymerization initiators include oil-soluble azo compounds [azobisdimethylvaleronitrile, azobisisobutyronitrile, azobiscyclohexanecarbonitrile, etc.], and oil-soluble peroxides [benzoyl peroxide, cumene hydroxyl peroxide, oxide etc.] and other radical polymerization initiators.

The amount of polymerization initiator used is preferably 0.001 to 2 parts by weight, more preferably 0.005 to 1% by weight, based on 100 parts by weight of the polymerizable monomer.

The polymerization temperature and polymerization time can be appropriately adjusted depending on the composition of the polymerizable monomer, the type of polymerization initiator, and the like. For example, the polymerization temperature can be 20 to 90° C. (preferably 20 to 80° C.), and the polymerization time can be 1 to 12 hours (preferably 1 to 10 hours).

(Step 3)
Step 3 is the step of adding a phase change agent to the polymer emulsion.

Phase change agents include highly hydrophilic surfactants [e.g., those with an HLB value of 9 to 20], cationic surfactants and nonionic surfactants described in Japanese Patent No. 2676483 and Japanese Patent Application Laid-Open No. 9-208802. Examples thereof include surfactants, and specific examples thereof include polyoxyalkylene lauryl ether (eg, "Emalmin HL-100" manufactured by Sanyo Chemical Industries, Ltd.). These can be used alone or in combination of two or more.

The amount of the phase change agent used is preferably 0.001 to 5 parts by weight, more preferably 0.005 to 1 part by weight, based on 100 parts by weight of the polymer emulsion, from the viewpoint of the stability and good phase transfer of the polymer emulsion. is.

The form of the polymer flocculant obtained by the production method of the present invention is preferably a water-in-oil emulsion. The proportion of the aqueous phase in the polymeric flocculant is preferably 7-83% by weight, more preferably 44-79% by weight, based on the weight of the polymeric flocculant.
The proportion of the hydrophobic dispersion medium in the polymer flocculant is preferably 15-88 wt%, more preferably 18-49 wt%, based on the weight of the polymer flocculant.

The product obtained after step 3 may be used as a polymer flocculant as it is, or a polymer obtained by adding water or other components (components other than the components contained in the aqueous phase and the oil phase). It may be used as a flocculating agent.

The polymer flocculant produced by the production method of the present invention contains a compound in which three or more molecules of an aliphatic carboxylic acid are bound to one molecule of an alkylene oxide adduct of a trihydric or higher polyol. The compound is derived from compound (A) contained in the emulsifier composition of the present invention.

The content of a compound in which 3 or more molecules of an aliphatic carboxylic acid are bonded to 1 molecule of an alkylene oxide adduct of a polyol having a valence of 3 or more in the polymer flocculant maintains the quality and environmental load as a polymer flocculant. From the viewpoint of suppressing , it is preferably 0.5 to 15% by weight, more preferably 1 to 7% by weight, based on the weight of the polymer flocculant.

The polymer flocculant produced by the production method of the present invention functions as a polymer flocculant together with a compound in which three or more molecules of an aliphatic carboxylic acid are bonded to one molecule of an AO adduct of a trihydric or higher polyol. Contains polymers.

Other components that the polymer flocculant may contain are, for example, selected from the group consisting of antifoaming agents, chelating agents, pH adjusters, surfactants, antioxidants, antiblocking agents, ultraviolet absorbers and preservatives. Additives that can be The method for incorporating these additives is not particularly limited, and examples include a method of stirring and mixing the polymer flocculant and these additives at room temperature or under heating. The amount of the additive used can be appropriately set in consideration of the intended use of the polymer flocculant and other components.

The polymer flocculant produced by the production method of the present invention can be used, for example, as a polymer flocculant for dehydration treatment of sludge such as sewage, construction soil, organic sludge generated in the treatment of industrial wastewater, and inorganic sludge. can be done. The polymer flocculant can be used by mixing sludge or wastewater with the polymer flocculant of the present invention to form flocs, followed by solid-liquid separation.

Uses other than the above uses of the polymer flocculant produced by the production method of the present invention include, for example, flocculants for excavation and muddy water treatment, papermaking agents (formation aids for the papermaking industry, drainage retention improvers, Drainability improver, paper strength agent, etc.), additives for increasing crude oil production (additives for secondary and tertiary recovery of crude oil), dispersants, scale inhibitors, coagulants, bleaching agents, thickeners, antistatic agents and A processing agent for textiles is mentioned.

EXAMPLES The present invention will be specifically described below with reference to Examples, but the present invention is not limited to these Examples. In addition, unless otherwise indicated, the part in an Example represents a weight part and % represents the weight%.

[Production Example 1: Production of tetraoleic acid ester of 30 mol EO adduct of sorbitol]
56 parts of sorbitol and 0.5 parts of potassium hydroxide are added to a 1 L autoclave equipped with a stirrer, thermometer, pressure gauge, pressure-resistant dropping bomb, pressure reduction and nitrogen introduction line, stirring is started, nitrogen is sealed, and the temperature is raised to 90°C. After heating, the pressure was reduced to 0.005 MPa, and the mixture was stirred for 1 hour. Then, the temperature was raised to 130±10° C., and 408 parts of ethylene oxide was successively added dropwise over 2 hours while maintaining the temperature at 4 to 6.5 kPa, followed by stirring for 1 hour until pressure equilibrium was reached at the same temperature. Thereafter, 20 parts of Kyoward 600 (manufactured by Kyowa Kagaku Co., Ltd.) was charged, subjected to adsorption treatment at 95° C. for 1 hour, and filtered to remove alkali metals. It was cooled to 60° C. and taken out to obtain an EO 30 mol adduct of sorbitol.
587 parts of EO30 mol adduct of sorbitol, 441 parts of oleic acid, 4 parts of p-toluenesulfonic acid, and 2 parts of diphosphite are charged into a reactor equipped with a stirring blade at room temperature, and the rotation speed of the stirring blade is set to 200 rpm. Nitrogen (purity of 99.999% or more; the same shall apply hereinafter) was passed through while stirring, and the temperature of the reaction system was raised to 120°C at the same time. Esterification was carried out while reducing the pressure in the system and distilling off water to obtain a tetraoleic acid ester [compound (A-1)] of an adduct of 30 mol of EO with sorbitol. In the compound (A-1), the polyol (sorbitol) has 5.0 alkyleneoxy groups (ethyleneoxy groups) per hydroxyl group. Compound (A-1) is a compound in which 4 molecules of oleic acid are bound to 1 molecule of a 30 mol EO adduct of sorbitol.

[Production Example 2: Production of Tetraoleic Acid Ester of 42 mol of EO and 2 mol of PO adduct of sorbitol]
39 parts of sorbitol and 0.5 parts of potassium hydroxide were added to a 1 L autoclave equipped with a stirrer, thermometer, pressure gauge, pressure-resistant dropping cylinder, pressure reduction and nitrogen introduction line, stirring was started, nitrogen was sealed, and the temperature was raised to 90°C. After heating, the pressure was reduced to 0.005 MPa, and the mixture was stirred for 1 hour. Then, the temperature was raised to 130±10° C., and a premix of 400 parts of ethylene oxide and 25 parts of propylene oxide was successively added dropwise over 2 hours while maintaining the temperature at 4 to 6.5 kPa, until pressure equilibrium was reached at the same temperature. Stirred for an hour. Thereafter, 20 parts of Kyoward 600 (manufactured by Kyowa Kagaku Co., Ltd.) was charged, subjected to adsorption treatment at 95° C. for 1 hour, and filtered to remove alkali metals. It was cooled to 60° C. and taken out to obtain an adduct of 42 mol of EO and 2 mol of PO of sorbitol.
Into a reactor equipped with a stirring blade, 670 parts of EO42 mol PO2 mol adduct of sorbitol, 353 parts of oleic acid, 4 parts of p-toluenesulfonic acid, and 2 parts of diphosphite are charged at room temperature, and the stirring blade is rotated at 200 rpm. Nitrogen (purity of 99.999% or more; the same shall apply hereinafter) was passed through while stirring at constant speed, and the temperature of the reaction system was raised to 120°C at the same time. Esterification was carried out while reducing the pressure in the system and distilling off water to obtain a tetraoleic acid ester [compound (A-2)] of an adduct of 42 mol of EO and 2 mol of PO of sorbitol. The number of alkyleneoxy groups (ethyleneoxy groups and propyleneoxy groups) per hydroxyl group of the polyol (sorbitol) in the compound (A-2) is 7.3. The compound (A-2) is a compound in which 4 molecules of oleic acid are bound to 1 molecule of an adduct of 42 mol of EO and 2 mol of PO of sorbitol.

[Production Example 3: Production of tetraoleic acid ester of EO 15 mol adduct of sorbitol]
(1) Add 100 parts of sorbitol and 0.5 parts of potassium hydroxide to a 1 L autoclave equipped with a stirrer, thermometer, pressure gauge, pressure-resistant dropping cylinder, decompression and nitrogen introduction line, and start stirring. After the temperature was raised to °C, the pressure was reduced to 0.005 MPa, and the mixture was stirred for 1 hour. Then, the temperature was raised to 130±10° C., and 364 parts of ethylene oxide was successively added dropwise over 2 hours while maintaining the temperature at 4 to 6.5 kPa, followed by stirring for 1 hour until pressure equilibrium was reached at the same temperature. Thereafter, 20 parts of Kyoward 600 (manufactured by Kyowa Kagaku Co., Ltd.) was charged, subjected to adsorption treatment at 95° C. for 1 hour, and filtered to remove alkali metals. It was cooled to 60° C. and taken out to obtain the EO15 adduct of sorbitol.
(2) Into a reaction tank equipped with a stirring blade, 443 parts of the 15 mol EO adduct of sorbitol produced in (1), 595 parts of oleic acid, 4 parts of p-toluenesulfonic acid, and 2 parts of diphosphite are charged at room temperature. Nitrogen (purity of 99.999% or more; hereinafter the same) was passed through while stirring with a stirring blade at a rotation speed of 200 rpm, and the temperature of the reaction system was raised to 120°C at the same time. Esterification was carried out while reducing the pressure in the system and distilling off water to obtain a tetraoleic acid ester [compound (A-3)] of an adduct of 15 mol of EO with sorbitol. In compound (A-3), the polyol (sorbitol) has 2.5 alkyleneoxy groups (ethyleneoxy groups) per hydroxyl group. Compound (A-3) is a compound in which 4 molecules of oleic acid are bound to 1 molecule of EO 15 mol adduct of sorbitol.

[Production Example 4: Production of hexaoleate ester of EO 15 mol adduct of sorbitol]
Into a reaction tank equipped with a stirring blade, 347 parts of the EO 15 mol adduct of sorbitol produced in Production Example 3 (1), 698 parts of oleic acid, 4 parts of p-toluenesulfonic acid, and 2 parts of diphosphorous acid were charged at room temperature. Nitrogen (purity of 99.999% or higher; hereinafter the same) was passed through while stirring with a stirring blade at a rotation speed of 200 rpm, and the temperature of the reaction system was raised to 130°C at the same time. Esterification was carried out while reducing the pressure in the system and distilling off water to obtain a hexaoleic acid ester [compound (A-4)] of an adduct of 15 mol of EO with sorbitol. In compound (A-4), the polyol (sorbitol) has 2.5 alkyleneoxy groups (ethyleneoxy groups) per hydroxyl group. Compound (A-4) is a compound in which 6 molecules of oleic acid are bound to 1 molecule of EO 15 mol adduct of sorbitol.

[Production Example 5: Production of Trilinoleic Acid Ester of Adduct of Sorbitol with 19 mol of EO and 1 mol of PO]
78 parts of sorbitol and 0.5 parts of potassium hydroxide were added to a 1 L autoclave equipped with a stirrer, thermometer, pressure gauge, pressure-resistant dropping cylinder, pressure reduction and nitrogen introduction line, stirring was started, nitrogen was sealed, and the temperature was raised to 90°C. After heating, the pressure was reduced to 0.005 MPa, and the mixture was stirred for 1 hour. Then, the temperature was raised to 130±10° C., and a premix of 361 parts of ethylene oxide and 25 parts of propylene oxide was successively added dropwise over 2 hours while maintaining the temperature at 4 to 6.5 kPa. Stirred for an hour. Thereafter, 20 parts of Kyoward 600 (manufactured by Kyowa Kagaku Co., Ltd.) was charged, subjected to adsorption treatment at 95° C. for 1 hour, and filtered to remove alkali metals. It was cooled to 60° C. and taken out to obtain an adduct of 19 mol of EO and 1 mol of PO of sorbitol.
Into a reactor equipped with a stirring blade, 578 parts of sorbitol EO 19 mole PO 1 mole adduct, 451 parts of linoleic acid, 4 parts of paratoluenesulfonic acid, and 2 parts of diphosphite are charged at room temperature, and the stirring blade is rotated at 200 rpm. Nitrogen (purity of 99.999% or more; the same shall apply hereinafter) was passed through while stirring at constant speed, and the temperature of the reaction system was raised to 120°C at the same time. Esterification was carried out while reducing the pressure in the system and distilling off water to obtain a trilinoleic acid ester [compound (A-5)] of an adduct of 19 mol of EO and 1 mol of PO of sorbitol. The number of alkyleneoxy groups (ethyleneoxy group and propyleneoxy group) per hydroxyl group of the polyol (sorbitol) in the compound (A-5) is 3.3. The compound (A-5) is a compound in which three molecules of linoleic acid are bound to one molecule of an adduct of 19 mol of EO and 1 mol of PO of sorbitol.

[Production Example 6: Production of tetralinoleic acid ester of EO13 adduct of diglycerin]
413 parts of EO 13 mol adduct of diglycerin [manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., SC-E750], 627 parts of linoleic acid, 4 parts of p-toluenesulfonic acid, 2 parts of diphosphite are placed in a reaction vessel equipped with a stirring blade. was introduced at room temperature, and nitrogen (purity of 99.999% or higher; hereinafter the same) was passed through while stirring with a stirring blade at a rotation speed of 200 rpm, and the temperature of the reaction system was raised to 130°C at the same time. Esterification was carried out while reducing the pressure in the system and distilling off water to obtain a tetralinoleic acid ester [compound (A-6)] of an EO13 adduct of diglycerin. In the compound (A-6), the polyol (diglycerin: tetravalent) has 3.3 alkyleneoxy groups (ethyleneoxy groups) per hydroxyl group. Compound (A-6) is a compound in which 4 molecules of linoleic acid are bound to 1 molecule of EO 13 mol adduct of diglycerin.

[Production Example 7: Production of trilaurate ester of EO 5 mole adduct of glycerin]
137 parts of glycerin and 0.5 part of potassium hydroxide were added to a 1 L autoclave equipped with a stirrer, thermometer, pressure gauge, pressure-resistant dropping cylinder, pressure reduction and nitrogen introduction line, stirring was started, nitrogen was sealed, and the temperature was raised to 90°C. After heating, the pressure was reduced to 0.005 MPa, and the mixture was stirred for 1 hour. Then, the temperature was raised to 130±10° C., and 327 parts of ethylene oxide was successively added dropwise over 2 hours while maintaining the temperature at 4 to 6.5 kPa, followed by stirring for 1 hour until pressure equilibrium was reached at the same temperature. Thereafter, 20 parts of Kyoward 600 (manufactured by Kyowa Kagaku Co., Ltd.) was charged, subjected to adsorption treatment at 95° C. for 1 hour, and filtered to remove alkali metals. It was cooled to 60° C. and taken out to obtain an EO 5 mol adduct of glycerin.
In a reactor equipped with a stirring blade, 363 parts of EO 5 mol adduct of glycerin, 700 parts of lauric acid, 4 parts of paratoluenesulfonic acid, and 2 parts of diphosphite are charged at room temperature, and the rotation speed of the stirring blade is set to 200 rpm. Nitrogen (purity of 99.999% or more; the same shall apply hereinafter) was passed through while stirring, and the temperature of the reaction system was raised to 120°C at the same time. Esterification was carried out while reducing the pressure in the system and distilling off water to obtain a trilauric acid ester [compound (A-7)] of an adduct of 5 mol of EO to glycerin. In the compound (A-7), the polyol (glycerin) has 1.7 alkyleneoxy groups (ethyleneoxy groups) per hydroxyl group. The compound (A-7) is a compound in which 3 molecules of lauric acid are bound to 1 molecule of a 5 mol EO adduct of glycerin.

[Production Example 8: Production of tribehenate ester of EO42 mol PO3 mol adduct of glycerin]
20 parts of glycerin and 0.5 part of potassium hydroxide are added to a 1 L autoclave equipped with a stirrer, thermometer, pressure gauge, pressure-resistant dropping cylinder, pressure reduction and nitrogen introduction line, stirring is started, nitrogen is sealed, and the temperature is raised to 90°C. After heating, the pressure was reduced to 0.005 MPa, and the mixture was stirred for 1 hour. Next, the temperature was raised to 130±10° C., and a premix of 406 parts of ethylene oxide and 38 parts of propylene oxide was successively added dropwise over 2 hours while maintaining the temperature at 4 to 6.5 kPa, until pressure equilibrium was reached at the same temperature for 1 hour. Stirred for an hour. Thereafter, 20 parts of Kyoward 600 (manufactured by Kyowa Kagaku Co., Ltd.) was charged, subjected to adsorption treatment at 95° C. for 1 hour, and filtered to remove alkali metals. It was cooled to 60° C. and taken out to obtain an adduct of glycerin with 42 mol of EO and 3 mol of PO.
In a reactor equipped with a stirring blade, 686 parts of EO42 mol PO3 mol adduct of glycerin, 332 parts of behenic acid, 4 parts of p-toluenesulfonic acid, and 2 parts of diphosphite are charged at room temperature, and the stirring blade is rotated at 200 rpm. Nitrogen (purity of 99.999% or more; the same shall apply hereinafter) was passed through while stirring at constant speed, and the temperature of the reaction system was raised to 120°C at the same time. Esterification was carried out while reducing the pressure in the system and distilling off water to obtain a tribehenic acid ester [compound (A-8)] of an adduct of 42 mol of EO and 3 mol of PO to glycerin. The number of alkyleneoxy groups (ethyleneoxy group and propyleneoxy group) per hydroxyl group of the polyol (glycerin) in the compound (A-8) is 15.0. The compound (A-8) is a compound in which three molecules of behenic acid are bound to one molecule of an adduct of 42 mol of EO and 3 mol of PO of glycerol.

[Production Example 9: Production of tristearate ester of 19 mol of EO and 1 mol of BO adduct of sorbitol]
77 parts of sorbitol and 0.5 parts of potassium hydroxide are added to a 1 L autoclave equipped with a stirrer, thermometer, pressure gauge, pressure-resistant dropping cylinder, pressure reduction and nitrogen introduction line, stirring is started, nitrogen is sealed, and the temperature is raised to 90°C. After heating, the pressure was reduced to 0.005 MPa, and the mixture was stirred for 1 hour. Then, the temperature was raised to 130±10° C., and a premix of 356 parts of ethylene oxide and 31 parts of butylene oxide was successively added dropwise over 2 hours while maintaining the temperature at 4 to 6.5 kPa. Stirred for an hour. Thereafter, 20 parts of Kyoward 600 (manufactured by Kyowa Kagaku Co., Ltd.) was charged, subjected to adsorption treatment at 95° C. for 1 hour, and filtered to remove alkali metals. It was cooled to 60° C. and taken out to obtain an adduct of 19 mol of EO and 1 mol of BO of sorbitol.
A reactor equipped with a stirring blade was charged with 577 parts of an adduct of 19 moles of EO and 1 mole of BO of sorbitol, 452 parts of stearic acid, 4 parts of p-toluenesulfonic acid, and 2 parts of diphosphorous acid at room temperature, and the stirring blade was rotated at 200 rpm. Nitrogen (purity of 99.999% or more; the same shall apply hereinafter) was passed through while stirring at constant speed, and the temperature of the reaction system was raised to 120°C at the same time. Esterification was carried out while reducing the pressure in the system and distilling off water to obtain a tristearate [Compound (A-9)] of an adduct of 19 mol of EO and 1 mol of BO of sorbitol. The number of alkyleneoxy groups (ethyleneoxy group and butyleneoxy group) per hydroxyl group of the polyol (sorbitol) in the compound (A-9) is 3.3. The compound (A-9) is a compound in which three molecules of stearic acid are bound to one molecule of an adduct of 19 mol of EO and 1 mol of BO of sorbitol.

[Production Example 10: Production of dioleate ester of EO 17 mol adduct of sorbitol]
91 parts of sorbitol and 0.5 parts of potassium hydroxide are added to a 1 L autoclave equipped with a stirrer, thermometer, pressure gauge, pressure-resistant dropping cylinder, pressure reduction and nitrogen introduction line, stirring is started, nitrogen is sealed, and the temperature is raised to 90°C. After heating, the pressure was reduced to 0.005 MPa, and the mixture was stirred for 1 hour. Then, the temperature was raised to 130±10° C., and 373 parts of ethylene oxide was successively added dropwise over 2 hours while maintaining the temperature at 4 to 6.5 kPa, followed by stirring for 1 hour until pressure equilibrium was reached at the same temperature. Thereafter, 20 parts of Kyoward 600 (manufactured by Kyowa Kagaku Co., Ltd.) was charged, subjected to adsorption treatment at 95° C. for 1 hour, and filtered to remove alkali metals. It was cooled to 60° C. and taken out to obtain an EO 17 mol adduct of sorbitol.
637 parts of EO 17 mol adduct of sorbitol, 387 parts of oleic acid, 4 parts of p-toluenesulfonic acid, and 2 parts of diphosphite are charged into a reactor equipped with a stirring blade at room temperature, and the rotation speed of the stirring blade is set to 200 rpm. Nitrogen (purity of 99.999% or more; the same shall apply hereinafter) was passed through while stirring, and the temperature of the reaction system was raised to 120°C at the same time. Esterification was carried out while reducing the pressure in the system and distilling off water to obtain a dioleic acid ester [compound (A'-1)] of an adduct of 17 mol of EO with sorbitol. The number of alkyleneoxy groups (ethyleneoxy groups) per hydroxyl group of the polyol (sorbitol) in the compound (A'-1) is 2.8. Compound (A'-1) is a compound in which two molecules of oleic acid are bound to one molecule of EO 17 mol adduct of sorbitol.

[Production Example 11: Production of trilaurate ester of EO30 mol adduct of sorbitol]
733 parts of EO30 mol adduct of sorbitol, 293 parts of lauric acid, 4 parts of p-toluenesulfonic acid, and 2 parts of diphosphite are charged into a reactor equipped with a stirring blade at room temperature, and the rotation speed of the stirring blade is set to 200 rpm. Nitrogen (purity of 99.999% or more; the same shall apply hereinafter) was passed through while stirring, and the temperature of the reaction system was raised to 120°C at the same time. Esterification was carried out while reducing the pressure in the system and distilling off water to obtain a trilauric acid ester [compound (A'-2)] of an adduct of 30 mol of EO with sorbitol. The number of alkyleneoxy groups (ethyleneoxy groups) per hydroxyl group of the polyol (sorbitol) in the compound (A'-2) is 5.0. The compound (A'-2) is a compound in which three molecules of lauric acid are bound to one molecule of a 30 mol EO adduct of sorbitol.

[Production Example 12: Production of pentacapric acid ester of EO 15 mol adduct of sorbitol]
522 parts of EO 15 mol adduct of sorbitol, 534 parts of decanoic acid, 4 parts of p-toluenesulfonic acid, and 2 parts of diphosphite are charged into a reactor equipped with a stirring blade at room temperature, and the rotation speed of the stirring blade is set to 200 rpm. Nitrogen (purity of 99.999% or more; the same shall apply hereinafter) was passed through while stirring, and the temperature of the reaction system was raised to 120°C at the same time. Esterification was carried out while reducing the pressure in the system and distilling off water to obtain pentacapric acid ester [compound (A'-3)] of EO 15 mol adduct of sorbitol. The number of alkyleneoxy groups (ethyleneoxy groups) per hydroxyl group of the polyol (sorbitol) in the compound (A'-3) is 2.5. Compound (A'-3) is a compound in which 5 molecules of capric acid (decanoic acid) are bound to 1 molecule of EO 15 mol adduct of sorbitol.

[Production Example 13: Production of trilignocerate ester of EO 15 mol adduct of sorbitol]
445 parts of EO 15 mol adduct of sorbitol, 584 parts of lignoceric acid, 4 parts of p-toluenesulfonic acid, and 2 parts of diphosphite are charged into a reactor equipped with a stirring blade at room temperature, and the rotation speed of the stirring blade is set to 200 rpm. Nitrogen (purity of 99.999% or more; the same shall apply hereinafter) was passed through while stirring, and the temperature of the reaction system was raised to 120°C at the same time. Esterification was carried out while reducing the pressure in the system and distilling off water to obtain a trilignoceric acid ester [compound (A'-4)] of an adduct of 15 mol of EO with sorbitol. In the compound (A'-4), the polyol (sorbitol) has 2.5 alkyleneoxy groups (ethyleneoxy groups) per hydroxyl group. Compound (A'-4) is a compound in which three molecules of lignoceric acid are bound to one molecule of EO 15 mol adduct of sorbitol.

The emulsifiers listed in Table 1 are as follows.
Compound (A-1): tetraoleate ester of 30 mol EO adduct of sorbitol produced in Production Example 1 Compound (A-2): tetraoleate ester of 42 mol EO 2 mol adduct of sorbitol produced in Production Example 2 Compound (A-3): tetraoleate ester of EO 15 mol adduct of sorbitol produced in Production Example 3 Compound (A-4): hexaoleate ester of EO 15 mol adduct of sorbitol produced in Production Example 4 Compound ( A-5): Trilinoleic acid ester of EO19 mol PO 1 mol adduct of sorbitol produced in Production Example 5 Compound (A-6): Tetralinoleic acid ester compound of EO13 EO adduct of diglycerol produced in Production Example 6 ( A-7): Trilaurate ester of 5 mol EO adduct of glycerin produced in Production Example 7 Compound (A-8): Tribehenate ester of 42 mol EO 3 mol adduct of glycerol produced in Production Example 8 Compound (A- 9): Tristearate ester compound (A'-1) of EO 19 mol BO 1 mol adduct of sorbitol produced in Production Example 9: Dioleate compound (A') of EO 17 mol adduct of sorbitol produced in Production Example 10 -2): trilaurate ester of EO 30 mol adduct of sorbitol produced in Production Example 11 Compound (A'-3): pentacaprate ester of EO 15 mol adduct of sorbitol produced in Production Example 12 Compound (A'- 4): Trilignocerate ester of EO 15 mol adduct of sorbitol produced in Production Example 13 Compound (B-1): Glycerol monooleate [manufactured by Kao Corporation, Kao Rhodol MO-60]
Compound (B-2): monooleic acid ester of sorbitan EO 20 mol adduct [manufactured by Sanyo Chemical Industries, Ltd., Ionet T-80V]
Compound (B-3): sorbitan monooleate [Ionet S-80, manufactured by Sanyo Chemical Industries, Ltd.]
Compound (B-4): monococonut oil fatty acid ester of sorbitan [Ionet S-20, manufactured by Sanyo Chemical Industries, Ltd.]

Table 1 shows the types of emulsifiers (compounds) as well as the structures (types of polyols, types of polyols, The type and number of added moles of AO, the type and number of binding molecules of carboxylic acid), the HLB value and the added amount (parts) are shown. Although compounds (A'-1) to (A'-4) are not compound (A) in the present invention, they are used in place of compound (A), and are therefore described in the column of compound (A).
Table 1 shows the HLB value and the added amount (parts) of the compounds (B-1) to (B-4), and the HLB value and the total added amount (parts) of the emulsifier composition for the emulsifier composition.

[Example 1]
In a vessel, 197.1 parts of 50% acrylamide aqueous solution, 511 parts of 79% dimethylaminoethyl acrylate methyl chloride quaternary salt, 23.3 parts of ion-exchanged water and 0.006 parts of methylene bisacrylamide were added at room temperature (20 to 25 ° C.) to prepare a monomer solution (aqueous phase). In another vessel, 253 parts of isoparaffin as a hydrophobic dispersion medium and 15 parts of the compound (A-1) obtained in Production Example 1 were charged to prepare an oil phase. The entire amount of the oil phase was added to the aqueous phase, and the mixture was stirred with a homomixer at a rotation speed of 8000 rpm for 2 minutes to obtain a monomer emulsion (water-in-oil emulsion). The emulsifiability of the resulting monomer emulsion was evaluated by the method described below.
The total amount of the monomer emulsion was charged into a reaction tank equipped with a stirring blade, and nitrogen (purity of 99.999% or more; the same applies hereinafter) was passed through while the stirring blade was being stirred at a rotational speed of 250 rpm. The temperature was raised to After sufficient nitrogen substitution (dissolved oxygen concentration of 20 ppb or less), radical polymerization initiator (2,2'-azobis (2-methylpropionamidine) dihydrochloride, "V-50" manufactured by Wako Pure Chemical Industries, Ltd.) 0 .4 parts were added. After that, stirring was continued at 50° C. for 1 hour to effect reverse phase emulsion polymerization. The temperature was raised to 70° C. and held for 1 hour, and then cooled to room temperature to obtain a polymer emulsion containing a polymer obtained by polymerizing a polymerizable monomer. A portion of the resulting polymer emulsion was subjected to a foreign matter amount measurement test.
While stirring 100 parts of the polymer emulsion at a rotation speed of 600 rpm, 0.5 parts of a phase change agent (polyoxyalkylene lauryl ether, "Emalmin HL-100" manufactured by Sanyo Chemical Industries, Ltd.) is added, and a polymer flocculant is added. Obtained. The obtained polymer flocculant was evaluated for phase inversion.
Each evaluation result is shown in Table 1.

[Example 2]
In Example 1, instead of 15 parts of compound (A-1), 20 parts of compound (A-2) and 10 parts of compound (B-1) obtained in Production Example 2 were used. A monomer emulsion, a polymer emulsion and a polymer flocculant were produced by the same operation as in 1 and evaluated by the same method as in Example 1. Each evaluation result is shown in Table 1.

[Example 3]
In Example 1, instead of 15 parts of compound (A-1), 13 parts of compound (A-3) and 17 parts of compound (B-2) obtained in Production Example 3 were used. A monomer emulsion, a polymer emulsion and a polymer flocculant were produced by the same operation as in 1 and evaluated by the same method as in Example 1. Each evaluation result is shown in Table 1.

[Example 4]
In Example 1, instead of 15 parts of compound (A-1), 15 parts of compound (A-4) and 15 parts of compound (B-2) obtained in Production Example 4 were used. A monomer emulsion, a polymer emulsion and a polymer flocculant were produced by the same operation as in 1 and evaluated by the same method as in Example 1. Each evaluation result is shown in Table 1.

[Example 5]
Example 1 except that 18 parts of compound (A-5) and 12 parts of (B-3) obtained in Production Example 5 were used instead of 15 parts of compound (A-1) in Example 1. A monomer emulsion, a polymer emulsion and a polymer flocculant were produced by the same operation as in Example 1 and evaluated by the same method as in Example 1. Each evaluation result is shown in Table 1.

[Example 6]
In Example 1, instead of 15 parts of compound (A-1), 10 parts of compound (A-1) and 10 parts of compound (A-6) obtained in Production Example 6 were used. A monomer emulsion, a polymer emulsion and a polymer flocculant were produced by the same operation as in 1 and evaluated by the same method as in Example 1. Each evaluation result is shown in Table 1.

[Example 7]
Example 1 except that 45 parts of compound (A-7) and 5 parts of (B-2) obtained in Production Example 7 were used instead of 15 parts of compound (A-1) in Example 1. A monomer emulsion, a polymer emulsion and a polymer flocculant were produced by the same operation as in Example 1 and evaluated by the same method as in Example 1. Each evaluation result is shown in Table 1.

[Example 8]
Example 1, except that 4 parts of compound (A-8) and 36 parts of (B-4) obtained in Production Example 8 were used instead of 15 parts of compound (A-1). A monomer emulsion, a polymer emulsion and a polymer flocculant were produced by the same operation as in Example 1 and evaluated by the same method as in Example 1. Each evaluation result is shown in Table 1.

[Example 9]
Example 1 except that 8 parts of compound (A-9) and 32 parts of (B-4) obtained in Production Example 9 were used instead of 15 parts of compound (A-1) in Example 1. A monomer emulsion, a polymer emulsion and a polymer flocculant were produced by the same operation as in Example 1 and evaluated by the same method as in Example 1. Each evaluation result is shown in Table 1.

[Comparative Example 1]
In Example 1, the same operation as in Example 1 was performed except that 30 parts of compound (A'-1) was used instead of 15 parts of compound (A-1). As a result, a monomer emulsion was formed without emulsification. I didn't get it. Therefore, it was not possible to evaluate the amount of foreign matter in the polymer emulsion and the phase inversion of the polymer flocculant. In Table 1, the evaluation results for the amount of foreign matter generated and the evaluation results for the phase inversion are marked with "-".

[Comparative Example 2]
In Example 1, the same operation as in Example 1 was performed except that 30 parts of compound (A'-2) was used instead of 15 parts of compound (A-1). As a result, a monomer emulsion was formed without emulsification. I didn't get it. Therefore, it was not possible to evaluate the amount of foreign matter in the polymer emulsion and the phase inversion of the polymer flocculant. In Table 1, the evaluation results for the amount of foreign matter generated and the evaluation results for the phase inversion are marked with "-".

[Comparative Example 3]
In Example 1, the same operation as in Example 1 was performed except that 30 parts of compound (B-3) was used instead of 15 parts of compound (A-1), and a monomer emulsion, a polymer emulsion and polymer aggregation were prepared. A formulation was prepared and evaluated in the same manner as in Example 1. Each evaluation result is shown in Table 1.

[Comparative Example 4]
In Example 1, the same operation as in Example 1 was performed except that 18 parts of compound (B-3) and 12 parts of compound (B-2) were used instead of 15 parts of compound (A-1), A monomer emulsion, a polymer emulsion and a polymer flocculant were produced and evaluated in the same manner as in Example 1. Each evaluation result is shown in Table 1.

[Comparative Example 5]
In Example 1, the same operation as in Example 1 was performed except that 30 parts of compound (A'-3) was used instead of 15 parts of compound (A-1). , and a polymer emulsion was not obtained. Therefore, it was not possible to evaluate the amount of foreign matter in the polymer emulsion and the phase inversion of the polymer flocculant. In Table 1, the evaluation results for the amount of foreign matter generated and the evaluation results for the phase inversion are marked with "-".

[Comparative Example 6]
In Example 1, the same operation as in Example 1 was performed except that 30 parts of compound (A'-4) was used instead of 15 parts of compound (A-1), and a monomer emulsion, a polymer emulsion and a polymer were prepared. A flocculant was produced and evaluated in the same manner as in Example 1. Each evaluation result is shown in Table 1.

[Evaluation of Emulsifiability of Monomer Emulsion]
The monomer emulsion of each example was allowed to stand at room temperature (25° C.) for 10 minutes and visually observed. Emulsifiability of the monomer emulsion was evaluated according to the following criteria.
(Evaluation criteria)
A: No phase separation observed B: Phase separation observed

[Measurement of Foreign Matter Amount in Polymer Emulsion]
If the stability of the emulsion is poor during polymerization, aggregates (foreign matter) of emulsion particles may occur. The amount of foreign matter generated was measured by the following method.
20 g of the precisely weighed polymer emulsion was filtered through a #100 mesh stainless wire mesh, and the emulsion attached to the wire mesh was washed away with a hydrocarbon oil in which 10% by mass of sorbitan sesquioleate was dissolved. The oil content was thoroughly wiped off with a paper towel, and the mass of the residue on the wire mesh was measured. Using the measured mass, the foreign matter amount (% by mass) was calculated according to the following formula (2). Polymerization stability is better when the amount of foreign matters (% by mass) is smaller, and polymerization stability is worse when the amount is larger.
(mass of residue / amount of emulsion subjected to filtration) × 100 = amount of foreign matter (% by mass) (2)

[Evaluation of inversion phase]
Jar tester [manufactured by Miyamoto Riken Kogyo Co., Ltd., model JMD-6HS-A, hereinafter the same. ] Attach one plate-shaped polyvinyl chloride stirring blade (diameter 5 cm, height 2 cm, thickness 0.2 cm) to the stirring rod, take 500 g of ion-exchanged water at 21 ° C. in a 500 mL beaker, and set it in a jar tester. did. While stirring the jar tester at a rotation speed of 300 rpm, it was confirmed that a stable vortex was generated, and the weight (W) of the polymer flocculant calculated by the following formula (3) was added at once, and the vortex disappeared. The time (seconds) required for the water surface to become horizontal was measured and evaluated according to the following criteria. The shorter the time, the better the phase inversion.
Weight W = (500 g x 0.5%) / polymer concentration (3)
In formula (3), the concentration of the polymer is the concentration (% by weight) of the polymer in the polymer emulsion, and the polymer obtained by polymerizing the polymerizable monomer based on the total weight of the polymer emulsion (Example 1 means the weight ratio of a polymer of acrylamide and dimethylaminoethyl acrylate methyl chloride quaternary salt).

As shown in Table 1, an emulsifier containing a compound in which three or more molecules of an aliphatic carboxylic acid are bonded to one molecule of an alkylene oxide adduct of a trihydric or higher polyol and having an HLB value of 5 to 12. According to the examples using the composition, both inverse emulsification and phase inversion can be achieved, and the amount of foreign matter generated is small. Therefore, according to the present invention, it is possible to provide an emulsifier composition that can achieve both reverse phase emulsification and phase inversion without increasing the amount of emulsifier used.

Claims (5)

A compound in which three or more molecules of an aliphatic carboxylic acid having 12 to 22 carbon atoms are ester-bonded to one molecule of an alkylene oxide adduct of a trihydric or higher polyol,
An emulsifier composition for inverse emulsion polymerization, wherein the compound has an HLB value of 5 to 12. 2. The emulsifier composition for inverse emulsion polymerization according to claim 1, wherein the alkylene oxide adduct of a trihydric or higher polyol is an alkylene oxide adduct of a tetrahydric or higher polyhydric alcohol. The emulsifier for reverse phase emulsion polymerization according to claim 1 or 2, wherein the alkylene oxide adduct of a trihydric or higher polyol is a compound obtained by adding an alkylene oxide having 2 to 4 carbon atoms to a trihydric or higher polyol. Composition. The emulsifier composition for inverse emulsion polymerization according to any one of claims 1 to 3, wherein the alkylene oxide adduct of a trihydric or higher polyol is an alkylene oxide adduct of a polyol having 3 to 6 carbon atoms. A method for producing a polymer flocculant, wherein the emulsifier composition according to any one of claims 1 to 4 is used to produce a polymer flocculant by a reverse phase emulsion polymerization method.