JP2002249471A - Production method of ester - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an unsaturated carboxylic acid amino alcohol ester in which by-products are less formed. SOLUTION: This is a method for producing an α,β-unsaturated carboxylic acid amino alcohol ester or its ketimine compound by the transesterification of an unsaturated carboxylic acid and an amino alcohol or its ketimine compound. In this case, characteristically, the transesterification is carried out in the presence of a titanium catalyst represented by the following general formula: O=Ti[OCOQCOOM(1/n)]2 (wherein Q is direct bond or dicarboxylic acid residue, M is an alkaline metal or an alkaline earth metal and n, a valency of M, is 1 or 2).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing an ester. More specifically, the present invention relates to a method for producing an ester having less by-products.

[0002]

2. Description of the Related Art α, β obtained by transesterification of α, β-unsaturated carboxylic acid ester with amino alcohol
-Unsaturated carboxylic acid amino alcohol esters are important as ester monomers which are raw materials for polymer flocculants and the like. As the catalyst in the transesterification reaction, a conventional alkali catalyst (sodium hydroxide, potassium hydroxide,
Sodium methylate, potassium-t-butoxide, sodium aluminum hydride, etc., acid catalyst [protic acid (sulfuric acid, paratoluenesulfonic acid, methanesulfonic acid, etc.), Lewis acid (zinc chloride, aluminum chloride, etc.)
And metal catalysts (such as dibutyltin dilaurate, manganese acetate, lead alkoxide, and nickel acetylacetone complex).

[0003]

However, the catalysts in the above-mentioned prior art have low catalytic activity and require a large amount of catalyst, which causes coloring and odor of the obtained ester. When an acid catalyst was used, there was a problem of corrosion of the reactor. Further, in the transesterification reaction using an alkali catalyst, a large amount of the carboxylic acid ester which has undergone an addition reaction to the carbon-carbon double bond of the α, β-unsaturated carboxylic acid ester is converted from the raw material amino alcohol or the alcohol formed by the transesterification during the reaction. By-product. This by-product hindered the polymerization reaction of the α, β-unsaturated carboxylic acid aminoalcohol ester, and required a great deal of labor for purification because it had a serious adverse effect on the quality of the polymer. Therefore, it has been a long-standing problem to selectively carry out the transesterification reaction.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have reached the present invention. That is, the present invention provides an ester (a) represented by the general formula (1)
And an amino alcohol (b) represented by the general formula (2) or a ketimine compound thereof (b ′) are subjected to a transesterification reaction to obtain an α, β-unsaturated carboxylic acid amino alcohol ester (A) or a ketimine compound thereof (A ') In the method for producing the titanium catalyst (c) represented by the general formula (3):
G-CX = CZ (COOR ¹ ) (1) HO—R ⁴ —NR ² R ³ (2) O = Ti (OCOQCOOM _{1 / n)} ) ₂ (3) wherein G, X and Z are each independently H and have 1 carbon atom
An atom or group selected from a hydrocarbon group and a carboxylate group of from 20 to 20; R ¹ is a hydrocarbon group of 1 to 20 carbon atoms; R ² and R ³ are the same or different hydrocarbon groups of 1 to 20 carbon atoms; R ² and R ³ may combine to form a divalent group which may have an ether bond to form a ring together with N; R ⁴ is a divalent carbon having 2 to 20 carbon atoms A hydrogen group; M is an alkali metal or alkaline earth metal; n is M
Q represents a direct bond or a dicarboxylic acid residue. A method for producing an α, β-unsaturated carboxylic acid amino alcohol ester (A), comprising hydrolyzing the (A ′) obtained by the production method; A method for producing an ester salt for producing an α, β-unsaturated carboxylic acid amino alcohol ester salt (B) by summing or quaternizing; (A) and / or (B) obtained by the production method and optionally other A method for producing a polymer which is obtained by copolymerizing a monomer and neutralizing or quaternizing as required when (A) is used; General formula (1)
And α, β by reacting a polymer having a monomer composed of a carboxylic acid ester (a) represented by the following formula with an amino alcohol (b) represented by the general formula (2) or a ketiminated compound (b ′) thereof. In the method for producing an unsaturated carboxylic acid amino alcohol ester polymer (J) or a ketiminated compound (J ′) thereof, a transesterification reaction is performed in the presence of a titanium catalyst (c) represented by the general formula (3). G-CX = CZ (COOR ¹ ) (1) HO—R ⁴ —NR ² R ³ (2) O = Ti (OCOQCOOM _{1 / n} ) ₂ (3) , G, X and Z each independently represent H, carbon number 1
An atom or group selected from a hydrocarbon group and a carboxylate group of from 20 to 20; R ¹ is a hydrocarbon group of 1 to 20 carbon atoms; R ² and R ³ are the same or different hydrocarbon groups of 1 to 20 carbon atoms; R ² and R ³ may be bonded to each other to form a divalent group optionally having an ether group to form a ring together with N; R ⁴ is a divalent carbon having 2 to 20 carbon atoms A hydrogen group; M is an alkali metal or alkaline earth metal; n is M
Q represents a direct bond or a dicarboxylic acid residue. A method for producing an α, β-unsaturated carboxylic acid amino alcohol ester polymer (J), comprising hydrolyzing (J ′) obtained by the production method; (J) obtained by the production method A method for producing an α, β-unsaturated carboxylic acid amino alcohol ester polymer (K), which is produced by neutralizing or quaternizing
G-CX = CZ (COOR ⁴ —NR ² R ³ ) (4) Neutralizing or quaternizing the amino group of the ester; An organic acid salt, an inorganic acid salt or a quaternary ammonium salt obtained by polymerizing the ester and / or a monomer comprising the salt of the ester, wherein the content of by-products is based on the weight of the ester unit in the polymer. 10% or less based on the above; and a polymer coagulant, a paper processing agent, a fiber processing agent, a soil improvement agent, or a tertiary recovery of petroleum comprising a polymer obtained by the method for producing the polymer. It is a polymer.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The hydrocarbon groups of G, X and Z in the general formula (1) include aliphatic, alicyclic and aromatic (aliphatic) hydrocarbon groups. As the aliphatic hydrocarbon group, a linear or branched saturated hydrocarbon (methyl,
Ethyl, n- and i-propyl, n-, i-, t- and sec-butyl, amyl, hexyl, octyl, decyl, dodecyl, octadecyl, eicosyl) groups,
And unsaturated hydrocarbons (allyl, methallyl, crotyl,
Hexenyl, octenyl, decenyl, dodecenyl, octadecenyl, eicosenyl, propargyl, butynyl,
Hexynyl, octynyl, decynyl, dodecynyl, octadecynyl, eicosinyl and the like) groups.

Examples of the alicyclic hydrocarbon group include a saturated hydrocarbon group (eg, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, cyclododecyl) and an unsaturated hydrocarbon group (eg, cyclobutenyl, cyclopentenyl,
Cyclohexenyl, methylcyclohexenyl, cyclododecenyl, etc.) groups. Examples of the aromatic (aliphatic) hydrocarbon group include aromatic hydrocarbon groups such as phenyl, toluyl, xylyl, mesityl, cumenyl, butylphenyl, nonylphenyl, dodecylphenyl, naphthyl, and methylnaphthyl. Group, anthracenyl group; araliphatic hydrocarbon group such as benzyl group,
And a phenethyl group.

As R ¹ in the general formula (1), there can be mentioned aliphatic, alicyclic and araliphatic hydrocarbon groups among those exemplified as the aforementioned hydrocarbon groups of G, X and Z. Further, as the ester group of G, X and Z,
The same as COOR ¹ in the general formula (1) can be mentioned. Specific examples of the α, β-unsaturated carboxylic acid constituting (a) in the present invention include monocarboxylic acids (acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid,
Dicarboxylic acids (such as maleic acid, methylmaleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid and cinnamic acid); and trivalent or tetravalent acids. (Α, β-dicarboxyacrylic acid and the like).

Specific examples of the alcohol constituting (a) include aliphatic (methyl, ethyl, n- and i-propyl, n-, i-, t- and sec-butyl, amyl,
Decyl, allyl, methallyl, crotyl, hexenyl, octenyl, propargyl, butynyl, hexynyl, octynyl, etc.) alcohols; alicyclic (cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl)
Cyclododecyl, cyclobutenyl, cyclopentenyl,
Cyclohexenyl) alcohol; araliphatic (benzyl, phenethyl, etc.) alcohol; Among these alcohols, preferred are alcohols having 1 to 5 carbon atoms, more preferred are ethyl alcohol, and particularly preferred is methyl alcohol, from the viewpoint that removal to the outside of the system is easy during the transesterification reaction in the subsequent step. .

The synthesis method of (a) is based on the above α, β
-Using an unsaturated carboxylic acid and an alcohol without a solvent or a solvent such as benzene, toluene or N-hexane,
Dehydration esterification reaction using an acid catalyst such as sulfuric acid or paratoluenesulfonic acid, after converting unsaturated carboxylic acid to acid chloride or acid anhydride, without solvent or pyridine, triethylamine, dimethylbenzylamine, etc. And α, β-unsaturated amide obtained by reacting fuming sulfuric acid with a cyanohydrinated compound obtained by adding hydrogen cyanide to an aldehyde or ketone, with the alcohol. And the like.

In the general formula (2), R ² and R ³ are the hydrocarbon groups exemplified for G, X and Z in the general formula (1), or R ² and R ³ are bonded to form an ether bond. with N becomes divalent group may be to form a ring (such as morpholino group), and examples of R ⁴ is,
Examples thereof include a divalent hydrocarbon group having 2 to 20 carbon atoms (such as an ethylene group, a butylene group, a 2-ethylhexylene group, a cyclohexylene group, and an octylene group).

Specific examples of the amino alcohol (b) represented by the general formula (2) include tertiary amino alcohols such as dimethylaminoethanol, dimethylaminopropanol, dimethylaminobutanol, morpholinoethanol and diisopropylaminoethanol. .

As the ketimine compound (b ′) of (b), a primary amino alcohol and a ketone [chain ketone (3 carbon atoms)
Chain ketones having 10 to 10 carbon atoms, for example, dialkyl ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, and ketones having a ring having 9 to 15 carbon atoms such as phenyl-2-propanone);
15, for example, cyclopentanone, cyclohexanone)
Alcohols (e.g., ketimine alcohols of monoethanolamine and methyl ethyl ketone, ketimine alcohols of monopropanolamine and methyl isobutyl ketone), and primary amino alcohols and aldehydes [chain aldehydes (carbon number 2-10 chain aldehydes such as acetaldehyde, butyraldehyde, isobutyraldehyde,
Valeraldehyde); Cyclic aldehyde (C7 to C15)
Having a ring of, for example, cyclohexane carbaldehyde, benzaldehyde), etc.] (aldehyde amine alcohols of monoethanolamine and butyraldehyde, aldehyde amine alcohols of monopropanolamine and isobutyraldehyde, etc.) And the like.

In the present invention, the alkali metal of M constituting the titanium catalyst (c) is lithium, sodium,
Potassium, rubidium and cesium are included, and alkaline earth metals include beryllium, calcium, magnesium and barium. Among these, from the viewpoint of catalytic activity, preferred are alkali metals, and more preferred are lithium and especially sodium,
Potassium.

As the dicarboxylic acid in the present invention, an aliphatic dicarboxylic acid [having 2 to 12 carbon atoms, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, maleic acid ,
Fumaric acid, itaconic acid, oxycarboxylic acid (tartaric acid, tartronic acid, malic acid, etc.)]; alicyclic dicarboxylic acid (C7-12, for example, cyclopentanedicarboxylic acid, cyclohexanedicarboxylic acid, cycloheptanedicarboxylic acid, etc.) An aromatic dicarboxylic acid (having 8 to 1 carbon atoms);
5, for example, phthalic acid, isophthalic acid, terephthalic acid, etc.). Q represents a direct bond when the dicarboxylic acid is oxalic acid, and represents a residue of each dicarboxylic acid in the case of the other dicarboxylic acids. As the residue in the case of a dicarboxylic acid having 3 or more carbon atoms, a residue having 1 to 1 carbon atoms is used.
0, a linear or branched saturated or unsaturated hydrocarbon group [alkylene (methylene, ethylene, propylene, hexylene, decylene, etc.) group, alkenylene (ethynylene, propenylene, hexenylene, etc.) group, cycloalkylene (cyclopentylene, cyclohexene) A silene, cycloheptylene, etc.) group, a cycloalkenylene (cyclohexenylene, etc.) group, an arylene (phenylene, etc.) group, etc.]. Of these, a direct bond and an alkylene group having 1 to 4 carbon atoms are preferable, and an alkylene group having 1 to 2 carbon atoms is more preferable, and a direct bond is particularly preferable.

Specific examples of the titanium catalyst (c) include alkali titanium oxalate (sodium, potassium, lithium and the like, the same applies hereinafter), alkylenedicarboxylic acid (C2-C12, for example, oxalic acid, malonic acid, succinic acid,
Glutaric acid and adipic acid) titanium alkali and the like. Of these, from the viewpoint of catalytic activity, preferred are titanium oxalate and titanium malonate, more preferred are titanium alkali oxalates, particularly titanium potassium oxalate and oxalate. It is sodium titanate.

The transesterification in the present invention can be carried out by a generally known method. That is, (a) and (b) or (b ′) are added without solvent or in a solvent in the presence of a polymerization inhibitor, and a titanium catalyst (c) is added. Perform an exchange reaction. The order of charging the raw materials and the like is not particularly limited, but preferably,
(A), (b) or (b ') when no solvent is used, and (a), (b) or (b') when a solvent is used
Is added first, and then a polymerization inhibitor and further a titanium catalyst (c) are added.

As the solvent, hydrocarbons (benzene, toluene, xylene, ethylbenzene, N-hexane, etc.)
Solvents. The transesterification in the present invention is usually carried out while removing the generated alcohol to the outside of the system. If necessary, these solvents can be used to azeotropically distill the alcohol with the solvent. When a solvent is used, the amount of the solvent used is usually 5 to 200% based on the total weight of (a) and (b) or (b ').

(A) and (b) in the transesterification reaction
Or the equivalent ratio to (b ′) is preferably (1 to 10) / 1, and more preferably (1.
1-5) / 1, especially (1.2-2) / 1.

As the polymerization inhibitor, phenolic (di-)
t-butylhydroxytoluene, hydroquinone, monomethylhydroquinone, pt-butylcatechol, etc., hindered amines (phenothiazine, phenyl-β-naphthylamine, diphenylamine, etc.), quinones (hydroquinone, p-methoxyphenol, etc.), mercaptans ( Ethylenethiourea), sulfur and copper compounds (copper powder, copper chloride, etc.). These polymerization inhibitors may be used alone or 2
More than one type may be used in combination. The amount of the polymerization inhibitor to be used is usually 0.01 to 1% by weight, preferably 0.05 to 0.8% by weight, more preferably 0.1 to 1% by weight based on (a).
0.5% by weight. The polymerization inhibitor is usually added to the reaction solution at the start of the reaction, but may be added to the reaction solution during the reaction.

The amount of the titanium catalyst (c) used is based on 1 equivalent (1 mol) of the α, β-unsaturated carboxylic acid ester (a) from the viewpoint of reactivity and low coloration of the resulting esterified product. It is preferably 10 ^-6 to 10 equivalents [1 equivalent corresponds to 1 mol of (c)], more preferably 10 ^{-5 to} 5 equivalents, and particularly preferably 10 ^-4 to 1 equivalent.

The transesterification in the present invention is usually carried out at normal pressure. However, the necessity due to (a), (b) or (b ') and the properties of the alcohol to be produced, such as the vapor pressure and boiling point, makes it necessary to apply pressure ( For example, a method of 0.05 to 0.5 MPa) or a reduced pressure (for example, -0.1 to -0.01 MPa) method can be employed. The reaction temperature of the transesterification is usually 2
The temperature is 0 to 130 ° C, preferably 50 to 125 ° C, more preferably 60 to 120 ° C, particularly 70 to 110 ° C.
To make it easier to remove the generated alcohol out of the system,
If necessary, an inert gas such as nitrogen or argon or a mixed gas of an inert gas and air may be bubbled in the liquid. The amount of bubbling is 20 to 300 L / min per 1,000 kg of the total weight of the reaction system.

The progress of the transesterification reaction can be determined by measuring the amount of distilled alcohol or measuring the unreacted (a), (b) or (b) by gas chromatography, high performance liquid chromatography, nuclear magnetic resonance spectrum, etc. of the reaction solution. ') Can be confirmed by quantification.

The ester (A) obtained by transesterification between (a) and (b) or (b '), and further, when (b') is used, is subjected to the production of a polymer as it is. Can be used for The ester (A) obtained above has a very low content of by-products, usually 10% by weight.
Hereinafter, the content is preferably 0 to 5% by weight, but if necessary, purification such as distillation, extraction, filtration, and adsorption treatment may be performed. In addition, unreacted (a),
(B) or (b ′) is not included. The by-product is a carboxylic acid ester formed by the addition reaction of the raw material amino alcohol (b) or the alcohol generated by the transesterification reaction to the carbon-carbon double bond of the α, β-unsaturated carboxylic acid ester. It can be confirmed by measurement using a nuclear magnetic resonance spectrum or the like.

The α, β-unsaturated carboxylic acid amino alcohol ester (A) obtained by the method of the present invention is neutralized with an organic or inorganic acid or quaternized with a quaternizing agent to obtain an α, β-unsaturated amino acid. The carboxylic acid amino alcohol ester salt (B) can be used. Here, obtained (B)
Is usually 98 to 100%, from the viewpoint of the stability of the ester bond of (B), preferably 99.5 to 100%. In the case of a quaternary salt, the quaternization ratio is usually 98 to 100%. ,
From the viewpoint of the stability of the ester bond of (B), preferably 9
9.5 to 100%.

Organic acids include aromatic (aliphatic), saturated or unsaturated aliphatic and saturated or unsaturated alicyclic mono- and poly (di, tri, tetra or higher).
-Carboxylic acids and sulfonic acids.

The aromatic (aliphatic) carboxylic acids include mono- and poly (di, tri, tetra or higher) carboxylic acids having 7 to 36 (preferably 7 to 18) carbon atoms. Specifically, monocarboxylic acids (such as benzoic acid, toluic acid, and naphthoic acid), dicarboxylic acids (such as isophthalic acid, terephthalic acid, and 2,6-naphthalenedicarboxylic acid), trivalent to tetravalent or higher polycarboxylic acids Acids (trimellitic acid, pyromellitic acid, etc.) and the like.

The saturated or unsaturated aliphatic carboxylic acids include mono- and poly- (di, tri, tetra or higher) carboxylic acids having 1 to 36 (preferably 1 to 18) carbon atoms. Specifically, monocarboxylic acids (formic acid, acetic acid, propionic acid, butyric acid, octylic acid, stearic acid, oleic acid, etc.), dicarboxylic acids (oxalic acid, malonic acid, succinic acid, adipic acid, etc.), and trivalent to 4
Or higher polycarboxylic acids, such as citric acid.

The saturated or unsaturated alicyclic carboxylic acids include mono- and poly (di, tri, tetra or higher) carboxylic acids having 4 to 36 (preferably 4 to 18) carbon atoms. Specifically, monocarboxylic acids (such as cyclobutanecarboxylic acid, cyclopentanecarboxylic acid, and cyclohexanecarboxylic acid) and dicarboxylic acids (such as cyclohexanedicarboxylic acid and a polymerized fatty acid obtained by polymerizing a fatty acid having 12 to 18 carbon atoms) are included. No.

Aromatic (fatty) sulfonic acids include mono- and poly (di, tri, tetra or higher) sulfonic acids having 6 to 36 (preferably 6 to 18) carbon atoms. Specific examples include benzenesulfonic acid, p-toluenesulfonic acid, xylenesulfonic acid, mesitylenesulfonic acid and dodecylbenzenesulfonic acid.

The saturated or unsaturated aliphatic sulfonic acids include mono- and poly (di, tri, tetra or higher) sulfonic acids having 1 to 36 (preferably 1 to 18) carbon atoms. Specific examples include methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, dodecylsulfonic acid, and sulfoalkyl (meth) acrylates such as sulfosuccinate. Examples of the saturated or unsaturated alicyclic sulfonic acid include a sulfonic acid having 3 to 36 carbon atoms (preferably 3 to 18 carbon atoms). Specific examples include cyclopropanesulfonic acid, cyclobutanesulfonic acid, cyclopentanesulfonic acid, and cyclohexanesulfonic acid. Examples of the inorganic acid include sulfuric acid, nitric acid, hydrochloric acid, and phosphoric acid. Among these, from the viewpoint of the cationic strength of the salt, preferred are inorganic acids,
Even more preferred are sulfuric acid, and especially hydrochloric acid.

Examples of the quaternizing agent include alkyl halides (1 to 36 carbon atoms, for example, methyl chloride, ethyl chloride, methyl bromide, etc.) and aralkyl halides (7 to 3 carbon atoms).
6, for example, benzyl chloride, etc.) and esters [2-36 carbon atoms, for example, sulfates (dimethyl sulfate, diethyl sulfate, etc.), carbonates (dimethyl carbonate, diethyl carbonate, etc.), sulfonates (methyl paratoluenesulfonate, etc.) And the like. Of these,
From the standpoint of the cationic strength of the salt, preference is given to dimethyl sulfate and also to methyl chloride.

(A) and / or (B) obtained by the method of the present invention may be added (co) polymerized by a known polymerization method by adding other known vinyl monomers if necessary, and when (A) is used, If necessary, neutralize with the above organic or inorganic acid, or quaternize with the quaternizing agent (co)
A polymer can be obtained. The content of the by-products in the (co) polymer is usually very low and may be 1% based on the weight of the (A) and / or (B) units in the (co) polymer.
0% by weight or less. (A) and / or (B);
The copolymerization ratio in the case of copolymerizing with other known vinyl monomers can be freely selected according to the purpose, but from the viewpoint of the performance of the copolymer, (A) and / or (B) and other known copolymers may be used. The content of (A) and / or (B) based on the total amount of all the monomers including the vinyl monomer is preferably 50 mol% or more, more preferably 70 mol% or more, and still more preferably 80 mol% to 100 mol. %.

The α, β-unsaturated carboxylic acid amino alcohol ester (co) polymer (J) in the present invention
Is obtained by a known polymerization method of a (co) polymer having a carboxylic acid ester (a) in the present invention and, if necessary, another known vinyl monomer (copolymerization ratio is the same as above) as a constitutional unit, and then obtaining titanium. It can be obtained by reacting with amino alcohol (b) or its ketimine compound (b ') in the presence of catalyst (c), and further hydrolyzing when (b') is used. In the above case, the amount of the titanium catalyst (c) used is (a) in the (co) polymer which is a precursor of (J).
Based on the number of ester units, preferably 10 ^-6 to
The equivalent is 10 equivalents [1 equivalent corresponds to 1 mol of (c)], more preferably 10 ^{-5 to} 5 equivalents, particularly preferably 10 ^-4 to 1 equivalent. Ester and the salt (K) of the α, β-unsaturated carboxylic acid amino alcohol ester (co) polymer (J) in the present invention may be neutralized or quaternized with the organic or inorganic acid of the (J). It can be obtained by quaternizing with an agent. Here, the degree of neutralization of the obtained (K) is usually 98 to 100%, preferably 99.5 to 100% from the viewpoint of the stability of the ester bond of the (co) polymer (K). In the case of the quaternization rate is usually 98 to 100%,
From the viewpoint of the stability of the ester bond of the (co) polymer (K), the content is preferably 99.5 to 100%.

The other known vinyl monomers include:
The following are mentioned. (A) Nonionic vinyl monomer [including (a) in the present invention] The following, and a mixture thereof: (a-1) (meth) acrylate derivative [hydroxyethyl (meth) acrylate, diethylene glycol mono (meth) Acrylate, polyethylene glycol (polymerization degree 51-100) mono (meth) acrylate, polyglycerol (polymerization degree 1-10) mono (meth) acrylate, etc.] (E2) (meth) acrylamide derivative [(meth) acrylamide, N -Methyl (meth) acrylamide, N-methylol (meth) acrylamide, etc.] (E3) unsaturated alcohol [vinyl alcohol,
(Meth) allyl alcohol, etc.] (E4) Nitrogen atom-containing vinyl monomer [N-vinyl-2-pyrrolidone, vinylimidazole, N-vinylsuccinimide, p-aminostyrene, N-vinylcarbazole, 2-vinylpyridine, vinyl Morpholine, 2
-Cyanoethyl (meth) acrylate, acrylonitrile, etc.]

(B) Anionic monomers The following acids and salts thereof [alkali metal salts, alkaline earth metal salts, ammonium salts and amines (having 1 to 2 carbon atoms)
0) Salts, etc.], and mixtures thereof. (B-1) Unsaturated carboxylic acid [(meth) acrylic acid, (anhydride) maleic acid, fumaric acid, itaconic acid, vinylbenzoic acid, etc.] ・ (b-2) Unsaturated sulfonic acid [aliphatic unsaturated sulfonic acid having 2 to 20 carbon atoms (eg vinyl sulfonic acid), aromatic unsaturated sulfonic acid having 6 to 20 carbon atoms (styrene sulfonic acid), sulfonic acid group-containing (meth) acrylate [Sulfoalkyl (C4 to C23) (meth) acrylate [sulfopropyl (meth) acrylate, sulfoethyl (meth) acrylate, 2- (meth) acryloyloxy-2,2-dimethylethanesulfonic acid, p- (meth)
Acryloyloxymethylbenzenesulfonic acid, methallylsulfonic acid], sulfonic acid group-containing (meth) acrylamide [N-sulfopropyl (meth) acrylamide, N
-Sulfoethyl (meth) acrylamide, 2-acryloylamino-2-methylpropanesulfonic acid, p- (meth) acryloylaminomethylbenzenesulfonic acid, etc.), alkyl (C1-20) (meth) allyl sulfosuccinate [methyl ((Meth) allyl sulfosuccinic acid ester etc.)] (b-3) (meth) acryloylpolyoxyalkylene (C1-6) sulfate [(meth) acryloylpolyoxyethylene (ethylene oxide added mole number 2-50) Sulfate ester etc.]

(C) Cationic monomers The following, salts thereof (for example, hydrochloride, sulfate, methyl chloride, dimethyl sulfate and benzyl chloride)], and mixtures thereof. (C-1) Nitrogen Atom-containing (meth) acrylate derivatives [N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-diethylaminopropyl ( (Meth) acrylate, etc.] (C-2) Nitrogen atom-containing (meth) acrylamide derivative [N, N-dimethylaminoethyl (meth) acrylamide, etc.] (C-3) Vinyl compound having amino group [vinylaniline, vinyl Pyridine, (meth) allylamine, diallylamine, dimethyl Allylamine, etc.], etc. (c -4) amine imide having a group [1,1,
1-trimethylamine (meth) acrylimide, 1,1
-Dimethyl-1-ethylamine (meth) acrylimide, 1,1-dimethyl-1- (2′-phenyl-2′-
Hydroxyethyl) amine (meth) acrylimide,
1,1,1-trimethylamine (meth) acrylimide etc.]

(D) Hydrophobic vinyl monomer The following (d-1) to (knee 2) and mixtures thereof (knee 1) (meth) acrylate having 4 to 23 carbon atoms [fat having 1 to 20 carbon atoms] (Meth) acrylates of aromatic and cycloaliphatic alcohols, such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth)
Acrylate, lauryl (meth) acrylate, octadecyl (meth) acrylate, cyclohexyl (meth)
Acrylate, epoxy group-containing (meth) acrylate having 4 to 20 carbon atoms, such as glycidyl (meth) acrylate]

(Knee 2) polypropylene glycol [propylene oxide (hereinafter abbreviated as PO) number of added moles 2
To 50] [monoalkyl (C1 to C20), monocycloalkyl (C3 to C12) or monophenyl ether] unsaturated carboxylic acid monoester [PO adduct of monool or diol, for example, monool (carbon (1-20) (meth) acrylic acid ester of PO adduct [ω-methoxypolypropylene glycol mono (meth)
Acrylate, ω-ethoxy polypropylene glycol mono (meth) acrylate, ω-propoxy polypropylene glycol mono (meth) acrylate, ω-butoxy polypropylene glycol mono (meth) acrylate, ω-cyclohexyl polypropylene glycol mono (meth) acrylate, ω-phenoxy polypropylene Glycol mono (meth) acrylate etc.], (meth) acrylic acid ester of diol (C1-20) PO adduct [ω-hydroxyethyl (poly) oxypropylene mono (meth) acrylate etc.] etc.]

(Knee 3) unsaturated nitrile having 3 to 20 carbon atoms [(meth) acrylonitrile and the like] (knee 4) unsaturated hydrocarbon monomer having 2 to 30 carbon atoms [ethylene, nonene, styrene, 1-methyl Styrene, etc.] ・ (Knee 5) unsaturated alcohol [vinyl alcohol,
(Meth) allyl alcohol] carboxylic acid ester having 2 to 20 carbon atoms (eg, vinyl acetate) (Knee 6) Halogen-containing monomer (eg, vinyl chloride) (acrylamide, acrylonitrile, N-vinylpyrrolidone, etc.), anionic vinyl Monomers (eg, sodium (meth) acrylate, sodium methallylsulfonate, sodium acrylamidomethylpropanesulfonate), cationic vinyl monomers (eg, diallylamine hydrochloride, dimethyldiallylammonium chloride, vinylpyridine), and mixtures thereof. .

Known polymerization methods for obtaining the polymer include emulsion polymerization, suspension polymerization, solution polymerization with water or an organic solvent, and the like. Solution polymerization is preferred from the viewpoint of the purity of the polymer. Examples of the solvent used in the solution polymerization include water, methanol, ethanol, isopropyl alcohol, toluene, acetone, tetrahydrofuran, and the like, and a mixture of these solvents. The concentration of the monomer with respect to the solvent is usually 10 to 80% by weight, preferably 1 to 80% by weight.
5 to 60% by weight.

Known polymerization initiators, for example, inorganic peroxides (ammonium persulfate, potassium persulfate, etc.), organic peroxides (t-butylperoxide, benzoyl peroxide, etc.), azo compounds [2,2 '
-Azobisisobutyronitrile, 4,4'azobis-
(4-cyanovaleric acid), etc.], and a redox initiator [combination of a peroxide (hydrogen peroxide, potassium persulfate, etc.) and a reducing agent (sodium bisulfite, ferrous sulfate, etc.)], and the like. . The amount of the polymerization initiator to be used is usually 0.1 to 10,000 ppm, preferably 0.5 to 5,000 ppm, more preferably 1 to 10,000 ppm based on the weight of the monomer.
2,000 ppm. The polymerization temperature is usually 20 to
The temperature is 100 ° C, preferably 30 to 80 ° C.

(A) and / or (A) obtained by the method of the present invention.
Alternatively, the molecular weight of the (co) polymer (B) and the (co) polymer (J) or (K) is represented by an intrinsic viscosity, which is typically 3 to 20 for cationic polymer flocculants.
dl / g, preferably 4 to 15 dl / g, and usually 3 to 15 dl / g, preferably 4 to 12 d for an amphoteric polymer flocculant.
1 / g. Here, the intrinsic viscosity is a value measured in a 1N aqueous solution of sodium nitrate at 30 ° C., and the unit is dl / g.

The (co) polymers (A) and / or (B) and the (co) polymers (J) and (K) obtained by the method of the present invention are polymer coagulants (sludge dewatering agents). , Wastewater treatment agents, etc.), paper processing agents (paper strength enhancers, etc.), fiber processing agents (antistatic agents, dye fixing agents, etc.), soil conditioners, and tertiary oil recovery polymers.

[0044]

The present invention will be described in detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.

Example 1 380 g (3.8 mol) of methyl methacrylate was placed in a 1 L glass reaction vessel equipped with a stirrer, thermometer and rectification column.
178 g (2 mol) of dimethylaminoethanol, 0.51 g (0.0014 mol) of potassium potassium oxalate, and 1.0 g of phenothiazine were charged, and the temperature at the top was adjusted to 60 to 64.
The reaction was carried out for 8 hours while keeping the temperature at 0 ° C and removing the azeotropic mixture of methanol and methyl methacrylate out of the system. The conversion of dimethylaminoethanol was 98%. −0.0
Unreacted methyl methacrylate was distilled off under reduced pressure at 9 MPa. The obtained amount was 312 g (yield 99.4%). High performance liquid chromatography (column; ODS φ7.5 × 2
50 mm, mobile phase; acetonitrile / water = 50/50)
Analysis revealed that the content of dimethylaminoethyl methacrylate was 99.5%. The Hazen unit color number was 50, and a slight amine odor was recognized.

Example 2 The same transesterification reaction as in Example 1 was carried out using 262 g (2 mol) of 2-morpholinoethanol in place of dimethylaminoethanol of Example 1. The gain is 39
The amount was 5 g (yield 99.2%), and as a result of analysis by high performance liquid chromatography, the content of 2-morpholinoethyl methacrylate was 99.4%. The Hazen unit color number was 60, and a slight amine odor was observed.

Comparative Example 1 In place of potassium titanium oxalate of Example 1, 3.0 g (0.056 mol) of sodium methoxide was used.
The same transesterification reaction as in Example 1 was performed. The gain is 3
The amount was 02 g (yield 96.2%), and as a result of analysis by high performance liquid chromatography, the content of dimethylaminoethyl methacrylate was 71.4%. From the nuclear magnetic resonance spectrum, it was confirmed that 15.2% of methyl α-methyl-β-dimethylaminoethoxypropionate and 13.4% of methyl α-methyl-β-methoxypropionate were by-produced. The Hazen unit color number was 150, and a strong peculiar smell was observed.

Comparative Example 2 The same transesterification reaction as in Example 1 was carried out using 2.5 g (0.018 mol) of zinc chloride instead of potassium potassium oxalate of Example 1. The amount obtained was 189 g (yield 60.2%). As a result of analysis by high performance liquid chromatography, the content of dimethylaminoethyl methacrylate was 89.7%. From the nuclear magnetic resonance spectrum,
It was confirmed that 6.4% of methyl α-methyl-β-dimethylaminoethoxypropionate and 3.9% of methyl α-methyl-β-methoxypropionate were by-produced.
The Hazen unit color number was 120, and a strong peculiar smell was observed.

Example 3 1 mol of methyl chloride was blown into a mixture of 1 mol of the monomer obtained in Example 1 and 200 g of water at 40 ° C. while stirring to obtain methacryloyloxyethyltrimethylammonium chloride. 500 g of water in this aqueous solution
Was replaced with nitrogen, placed in a glass container having an inner diameter of 30 cm and a depth of 5 cm, and replaced with nitrogen. Then, 0.1 g of ammonium persulfate was added and kept at 40 to 45 ° C.
The polymerization started immediately and was completed after one hour. The obtained polymer was taken out, cut into pieces, dried in a dryer at 100 ° C. to a solid content concentration of 90%, and then pulverized to obtain a powdery polymer. The colloid equivalent and the intrinsic viscosity at pH 4 of the polymer were measured. The colloid equivalent was titrated with an N / 400 polyvinyl potassium sulfate reagent using a toluidine blue indicator, and the point at which the measurement sample changed color from blue to reddish purple was defined as the titration end point. The intrinsic viscosity was measured in a 1N-NaNO ₃ aqueous solution at 30 ° C. 0.1% of the polymer
Ion exchange aqueous solution, N city sewage treatment plant excess sludge [pH
6.9, 2.3% TS (total solid content), 80% organic content) as a polymer, and a dehydration test was performed using a small belt press dehydrator to obtain a polymer. The moisture content of the cake was measured. The results are shown in Table 1.

Comparative Example 3 A polymer was synthesized in the same manner as in Example 3 except that the monomer obtained in Comparative Example 1 was used instead of the monomer obtained in Example 1 of Example 3. The same performance evaluation as in No. 3 was performed. The results are shown in Table 1.

[0051]

[Table 1]

From the results shown in Table 1, the polymer obtained in Example 3 shows a higher dehydration rate (lower cake water content) than the polymer obtained in Comparative Example 3, and has excellent performance as a polymer flocculant. You can see that it is.

[0053]

The present invention has the following effects. 1. A highly pure ester is obtained. 2. An ester with a very small amount of a catalyst and little coloring and odor is obtained. 3. No risk of corrosion of reactor. Therefore, the (co) polymer obtained from the high-purity ester as a raw material has high purity, and is used as a polymer flocculant, a paper processing agent, a fiber processing agent, a soil conditioner, or a tertiary oil recovery polymer. Extremely useful.

Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) // C07B 61/00 300 C07B 61/00 300 F term (reference) 4C056 AA02 AB01 AC03 EA04 EA07 4H006 AA02 AC48 BA10 BA32 BT12 4H039 CA66 CD90 4J100 AD00Q AJ00Q AL01P AL01Q AL02Q AL08P AL08Q AL16P AM02Q AM14Q AM21Q AP01Q AQ06Q BA08Q BA31P BA31Q BA55Q BA56Q BC79P CA01 CA04 HA31 JA11 JA13 JA15 JA18 JA67

Claims (12)

[Claims] An ester (a) represented by the general formula (1)
And an amino alcohol (b) represented by the general formula (2) or a ketimine compound thereof (b ′) are subjected to a transesterification reaction to obtain an α, β-unsaturated carboxylic acid amino alcohol ester (A) or a ketimine compound thereof (A ') In the method for producing the titanium catalyst (c) represented by the general formula (3):
A transesterification reaction in the presence of a compound. G-CX = CZ (COOR ¹ ) (1) HO—R ⁴ —NR ² R ³ (2) O = Ti (OCOQCOOM _{1 / n} ) ₂ (3) wherein G, X and Z are each independently H, carbon number 1
An atom or group selected from a hydrocarbon group and a carboxylate group of from 20 to 20; R ¹ is a hydrocarbon group of 1 to 20 carbon atoms; R ² and R ³ are the same or different hydrocarbon groups of 1 to 20 carbon atoms; R ² and R ³ may combine to form a divalent group which may have an ether bond to form a ring together with N; R ⁴ is a divalent carbon having 2 to 20 carbon atoms A hydrogen group; M is an alkali metal or alkaline earth metal; n is M
Q represents a direct bond or a dicarboxylic acid residue. ] 2. A method for producing an α, β-unsaturated carboxylic acid amino alcohol ester (A), comprising hydrolyzing (A ′) obtained by the production method according to claim 1. 3. An ester salt for producing an α, β-unsaturated carboxylic acid amino alcohol ester salt (B) by neutralizing or quaternizing (A) obtained by the production method according to claim 1 or 2. Production method. 4. The copolymer (A) and / or (B) obtained by the production method according to any one of claims 1 to 3 and another monomer as required, and when (A) is used, if necessary, A method for producing a polymer to be neutralized or quaternized. 5. A polymer comprising a monomer composed of a carboxylic acid ester (a) represented by the general formula (1) as a constituent unit and an amino alcohol (b) represented by the general formula (2) or a ketiminated compound thereof (b ′) ) To form an α, β-unsaturated carboxylic acid amino alcohol ester polymer (J)
Alternatively, in the method for producing the ketimine compound (J '), a transesterification reaction is carried out in the presence of a titanium catalyst (c) represented by the general formula (3). G-CX = CZ (COOR ¹ ) (1) HO—R ⁴ —NR ² R ³ (2) O = Ti (OCOQCOOM _{1 / n} ) ₂ (3) wherein G, X and Z are each independently H, carbon number 1
An atom or group selected from a hydrocarbon group and a carboxylate group of from 20 to 20; R ¹ is a hydrocarbon group of 1 to 20 carbon atoms; R ² and R ³ are the same or different hydrocarbon groups of 1 to 20 carbon atoms; R ² and R ³ may combine to form a divalent group which may have an ether bond to form a ring together with N; R ⁴ is a divalent carbon having 2 to 20 carbon atoms A hydrogen group; M is an alkali metal or alkaline earth metal; n is M
Q represents a direct bond or a dicarboxylic acid residue. ] 6. An α, β-unsaturated carboxylic acid amino alcohol ester polymer (J) comprising hydrolyzing the polymer (J ′) obtained by the production method according to claim 5.
Manufacturing method. 7. Production of an α, β-unsaturated carboxylic acid amino alcohol ester polymer (K) produced by neutralizing or quaternizing (J) obtained by the production method according to claim 5 or 6. Method. 8. The method according to claim 1, wherein the amount of (c) used is 10 ^-6 to 10 equivalents per equivalent of (a). 9. Obtained by the method according to claim 1 or 2,
An ester represented by the general formula (4) having a by-product content of 10% by weight or less. ^{G-CX = CZ (COOR 4} -NR 2 R 3) (4) 10. An organic acid salt, an inorganic acid salt or a quaternary ammonium salt obtained by neutralizing or quaternizing the amino group of the ester according to claim 9. 11. A polymer obtained by polymerizing a monomer comprising an ester according to claim 9 and / or a salt of the ester according to claim 10, wherein the content of by-products is 10% based on the weight of the ester unit in the polymer. % Polymer. 12. A tertiary recovery of a polymer flocculant, a paper processing agent, a fiber processing agent, a soil improvement agent, or petroleum comprising the polymer obtained by the method for producing a polymer according to any one of claims 4 to 8. For polymers.