JP2019044075A - Liquid overbased metal complex-containing composition and method for producing liquid overbased metal complex - Google Patents

Abstract

A method for producing a carboxylate / carbonate complex of a periodic table group 2 element by suppressing the formation of a carbonate precipitate, and a high quality periodic table having a low content of carbonate precipitates. Provided is a Group 2 element carboxylate / carbonate complex. A method of producing a liquid overbased metal complex having a carboxylate / carbonate complex structure of a metal atom of periodic table group 2 and / or a phenate / carbonate complex structure, wherein the production method is A hydroxide of a metal atom of the periodic table group 2, a hydrocarbon solvent having a boiling point of 150 ° C. or higher, a monohydric alcohol having 8 to 20 carbon atoms, a carboxyl group-containing compound and / or a phenol compound, and HLB A first step of mixing 10 or more surfactants to form a carboxylate and / or phenate of the metal atom, a carboxylate of the metal atom of Group 2 of the periodic table obtained in the first step, and Carbon dioxide is added to the phenate and / or phenate to form a carboxylate / carbonate complex structure of the metal atom and / or a phenate / carbonate complex structure Method for manufacturing a liquid overbased metal complex and a second step of made. [Selected figure] None

Description

The present invention relates to a liquid overbased metal complex-containing composition and a method for producing a liquid overbased metal complex. More specifically, the present invention relates to a liquid overbased metal complex-containing composition used as a heat resistance imparting agent or the like of a resin such as a vinyl chloride resin, and a method of producing a liquid overbased metal complex.

Chlorine-containing resins typified by polyvinyl chloride are highly flexible and easy to process, and conventionally used for various applications such as construction materials, automobile parts, home appliance parts, etc. in addition to various films, electric wires, pipes, resin window frames, etc. It is used. However, chlorine-containing resins have a problem in thermal stability, and since they are unstable in heat during processing and use and decomposition occurs by heating, stabilizers are generally used.
As a stabilizer, for example, an alkali or alkaline earth metal salt such as liquid overbased carboxylate / carbonate complex of barium is used (see Patent Documents 1 to 3.)

Patent No. 4251881 gazette Unexamined-Japanese-Patent No. 2016-41723 U.S. Pat. No. 4,665,117

The liquid overbased carboxylate / carbonate complex of barium is produced by mixing barium hydroxide, long chain alcohol and long chain carboxylic acid to form barium carboxylate etc. as described in the above-mentioned Patent Document 1 After that, carbon dioxide gas is introduced to produce a chelate complex. The carboxylate / carbonate complex of the periodic table group 2 element is produced by the same method, but in this method, an insoluble carbonate is likely to be formed as a precipitate when carbon dioxide gas is introduced. Since separation of such a carbonate and a carboxylate / carbonate complex is very complicated, the periodic table group 2 element can be generated without forming a precipitate of carbonate so that such separation does not occur. There is a need for a process that can produce carboxylate / carbonate complexes of

The present invention has been made in view of the above-mentioned present situation, and a method for producing a carboxylate / carbonate complex of a periodic table group 2 element while suppressing the formation of a precipitate of carbonate, and precipitation of carbonate It is an object of the present invention to provide a high quality periodic table group 2 carboxylate / carbonate complex having a low content of substances.

The present inventors examined a method for producing a carboxylate / carbonate complex of a periodic table group 2 element by suppressing the formation of a carbonate precipitate, and as a result, a hydroxide of a metal atom of the periodic table group 2 was obtained. And a first hydrocarbon solvent, a monohydric alcohol, a carboxyl group-containing compound, and a surfactant mixed to form a carboxylate of the metal atom, and The second step of adding carbon dioxide to the carboxylate of the metal atom of Group 2 of the periodic table to form a carboxylate / carbonate complex structure of the metal atom It is possible to produce a carboxylate / carbonate complex of a periodic table group 2 element by suppressing the formation thereof, and a phenolic compound in place of the carboxyl group-containing compound The same method but using, phenate / carbonate complex of the Group 2 metal atoms also found that it is possible to produce. The present inventors have also found that a composition comprising a liquid overbased metal complex having a carboxylate / carbonate complex structure of a metal atom of Group 2 of the periodic table and / or a phenate / carbonate complex structure thus produced. However, they have also found that they are different from the carboxylate / carbonate complex composition of the periodic table group 2 element produced by the conventional method, and have completed the present invention.

That is, the present invention is a composition comprising a liquid overbased metal complex having a carboxylate / carbonate complex structure of a metal atom of periodic table group 2 and / or a phenate / carbonate complex structure, wherein the composition is A liquid overbased metal complex-containing composition comprising the liquid overbased metal complex, a hydrocarbon solvent having a boiling point of 150 ° C. or more, a monohydric alcohol having 8 to 20 carbon atoms, and a surfactant having an HLB of 10 or more It is a thing. In addition, the concept of the liquid in this reaction system means the state which maintains a density close | similar to a solid in 0 degreeC-200 degreeC, and flows.

The metal atom of Group 2 of the periodic table is preferably at least one selected from the group consisting of calcium, barium, magnesium and strontium.

It is preferable that the said carboxylate is formed from a C8-C30 monovalent | monohydric carboxylic acid.

It is preferable that the said phenate is formed from a C9-C30 alkyl phenol.

The surfactant having an HLB of 10 or more is preferably decaglycerin fatty acid ester and / or sorbitan fatty acid ester.

The present invention is also a method for producing a liquid overbased metal complex having a carboxylate / carbonate complex structure of a metal atom of periodic table group 2 and / or a phenate / carbonate complex structure, which is a method for producing the same. A hydroxide of a metal atom of the periodic table group 2, a hydrocarbon solvent having a boiling point of 150 ° C. or higher, a monohydric alcohol having 8 to 20 carbon atoms, a carboxyl group-containing compound and / or a phenol compound, and HLB A first step of mixing at least 10 surfactants to form a carboxylate and / or phenate of the metal atom, and a carboxylate of a metal atom of Group 2 of the periodic table obtained in the first step And / or / or phenate / carboxylate complex structure of the metal atom by adding carbon dioxide to the phenate and / or phenate / carbonate complex structure It is also a method for manufacturing a liquid overbased metal complex and a second step of producing.

It is preferable that the said carboxyl group-containing compound is a C8-C30 monovalent | monohydric carboxylic acid.

The phenolic compound is preferably an alkylphenol having 9 to 30 carbon atoms.

The surfactant having an HLB of 10 or more is preferably decaglycerin fatty acid ester and / or sorbitan fatty acid ester.

The method for producing a liquid overbased metal complex of the present invention is capable of producing a carboxylate / carbonate complex of a periodic table group 2 element while suppressing the formation of a precipitate of a carbonate salt. It is a useful method that can also be used for industrial production of carboxylate / carbonate complexes of group elements. The liquid overbased metal complex-containing composition of the present invention is liquid, has high compatibility with the resin, and can be suitably used as a heat resistance imparting agent for chlorine-containing resins such as polyvinyl chloride.

Hereinafter, although an example of the present invention is explained concretely, the present invention is not limited only to the following descriptions, and it can change suitably and can apply it in the range which does not change the gist of the present invention.

<Liquid overbased metal complex-containing composition>
The liquid overbased metal complex-containing composition of the present invention contains a liquid overbased metal complex having a carboxylate / carbonate complex structure of a metal atom of Group 2 of the periodic table and / or a phenate / carbonate complex structure.
The carboxylate / carbonate complex structure of the metal atom of the periodic table group 2 is a structure in which the carboxylate of the metal atom of the periodic table group 2 and the carbonate of the metal atom of the periodic table group 2 form a complex. Although the detailed structure of this complex is not clear, it has a structure in which the metal atom of the carboxylate of the metal atom of the periodic table group 2 and the carbonate portion of the metal carbonate of the periodic table group 2 have some interaction It is estimated that And, in the liquid overbased metal complex-containing composition of the present invention, the periodic table around the carbonate of the metal atom of the periodic table group 2 in the hydrocarbon solvent having a boiling point of 150 ° C. or higher contained in the composition It is presumed that a reverse micelle structure is formed in which the carboxylate structure side of the metal atom of Group 2 is outside.
Similarly, the phenate / carbonate complex structure of the metal atom of periodic table group 2 means that the metal atom of phenate of the metal atom of periodic table group 2 and the carbonate portion of the metal carbonate of group 2 of periodic table mutually It is presumed to have a structure that has acted. In the liquid overbased metal complex-containing composition of the present invention, the periodic table No. 2 is contained around the carbonate of the metal atom of the periodic table group 2 in a hydrocarbon solvent having a boiling point of 150 ° C. or higher contained in the composition. It is presumed that a reverse micelle structure is formed with the phenate structure side of the metal atoms of the

The metal atom of Group 2 of the periodic table in the liquid overbased metal complex of the present invention is not particularly limited, but is preferably at least one selected from the group consisting of calcium, barium, magnesium and strontium. More preferably, it is at least one selected from the group consisting of calcium, barium and magnesium, and more preferably at least one selected from the group consisting of calcium and barium.

The carboxylate in the liquid overbased metal complex of the present invention may be formed from any carboxylic acid, but is preferably formed from a monovalent carboxylic acid having 8 to 30 carbon atoms. . If it is formed from such a carboxylic acid, complexation is likely to occur. More preferably, it is formed from a C10-C26 monovalent carboxylic acid, and still more preferably is formed from a C12-C22 monovalent carboxylic acid.
The carboxylate in the liquid overbased metal complex of the present invention may be formed from one type of carboxylic acid, or may be formed from two or more types of carboxylic acid.

Examples of the monovalent carboxylic acid used for the carboxylate in the liquid overbased metal complex of the present invention include caprylic acid, lauric acid, palmitic acid, stearic acid, behenic acid, oleic acid, linoleic acid, linolenic acid and the like. .

The phenate in the liquid overbased metal complex of the present invention may be formed from any phenolic compound, but is preferably formed from an alkylphenol having 9 to 30 carbon atoms. Complexation is likely to occur if it is formed from such a phenol compound. More preferably, it is formed from a C10-C26 alkylphenol, More preferably, it is formed from a C12-C20 alkylphenol.
The phenate in the liquid overbased metal complex of the present invention may be formed from one type of phenolic compound, or may be formed from two or more types of phenolic compound.

Examples of the phenolic compound used for the phenate in the liquid overbased metal complex of the present invention include butylphenol, octylphenol, nonylphenol and dodecylphenol.

The liquid overbased metal complex-containing composition of the present invention contains a hydrocarbon solvent having a boiling point of 150 ° C. or more, and preferably contains a hydrocarbon solvent having a boiling point of 170 ° C. or more. More preferably, it is a hydrocarbon-based solvent having a boiling point of 190 ° C. or more, and even more preferably a hydrocarbon-based solvent having a boiling point of 200 ° C. or more.
The boiling points in the present invention are all boiling points at 1 atm.

As a hydrocarbon solvent having a boiling point of 150 ° C. or higher, for example, Super Oil N-7 (hydrocarbon solvent manufactured by JX Energy Corporation: 180-360 ° C.), Super Oil N-22 (hydrocarbon solvent manufactured by JX Energy Corporation) : Various paraffin oils having a boiling point of 265 to 450 ° C., various process oils, etc. may be mentioned, and one or more of these may be used. Among these, super oil N-22 is preferable.

The liquid overbased metal complex-containing composition of the present invention contains a monohydric alcohol having 8 to 20 carbon atoms, preferably containing a monohydric alcohol having 10 to 18 carbon atoms. More preferably, it is a C12-C16 monohydric alcohol.

Examples of monohydric alcohols having 8 to 20 carbon atoms include octanol, nonanol, decanol, isodecanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol and the like. And one or more of these can be used. Among these, preferred are decanol, tridecanol and tetradecanol, and more preferred is tetradecanol.

The liquid overbased metal complex-containing composition of the present invention contains a surfactant having an HLB of 10 or more, and among them, a surfactant having an HLB of 12 or more is preferable. More preferably, the surfactant has an HLB of 14 or more. When the HLB is less than 10, it becomes difficult to stably obtain a liquid overbased metal complex.
The HLB (value) of the surfactant in the present invention is a value according to the Griffin method.

Examples of surfactants having an HLB of 10 or more include fatty acid esters of polyglycerin. As polyglycerin, what has 4-15 hydroxyl groups is preferable. More preferably, it has 6 to 13 hydroxyl groups, and still more preferably 8 to 11 hydroxyl groups.

As a fatty acid ester-bonded to polyglycerol, a fatty acid having 8 to 22 carbon atoms is preferable. More preferably, it is a C10-C20 fatty acid, More preferably, it is a C12-C18 fatty acid.
Specific examples of the fatty acid include higher fatty acids such as caprylic acid, lauric acid, myristic acid, stearic acid, oleic acid and behenic acid.

In the fatty acid ester of polyglycerin, the number of fatty acids esterified to polyglycerin is not particularly limited, but is preferably 1 to 3, more preferably 1 or 2, and most preferably 1. That is, as fatty acid esters of polyglycerin, monofatty acid esters of polyglycerin are most preferable.

Examples of the surfactant having an HLB of 10 or more include decaglycerin monoester, decaglycerin triester, hexaglycerin monoester, polyoxyethylene sorbitan ester and the like, and one or more of these may be used. Among them, decaglycerin fatty acid ester and / or sorbitan fatty acid ester are preferable. More preferably, it is an ester of C12-C22 fatty acid of decaglycerin and / or sorbitan, More preferably, it is a monoester of a C14-C18 fatty acid of decaglycerin and / or sorbitan.
When the HLB contains 10 or more of these as a surfactant, the liquid overbased metal complex of the present invention has high quality with few insolubles.

The content of the hydrocarbon solvent having a boiling point of 150 ° C. or more in the liquid overbased metal complex-containing composition of the present invention is 10 to 60 parts by weight with respect to 100 parts by weight of the liquid overbased metal complex contained in the composition Is preferred. More preferably, it is 20 to 50 parts by weight, still more preferably 30 to 40 parts by weight.

The content of the monohydric alcohol having 8 to 20 carbon atoms in the liquid overbased metal complex-containing composition of the present invention is 1 to 10 parts by weight with respect to 100 parts by weight of the liquid overbased metal complex contained in the composition Is preferred. More preferably, it is 2 to 9 parts by weight, still more preferably 3 to 8 parts by weight. Even if a C8 to C20 monohydric alcohol is used in a proportion of more than 10 parts by weight, the reaction promoting effect is small, and the reaction concentration may be small, which may cause the reaction to be inhibited.

The content of the surfactant having a HLB of 10 or more in the liquid overbased metal complex-containing composition of the present invention is 0.1 to 5.0 parts by weight with respect to 100 parts by weight of the liquid overbased metal complex contained in the composition. It is preferable that it is a weight part. More preferably, it is 0.3 to 3.0 parts by weight, still more preferably 0.5 to 2.0 parts by weight. When the content of the surfactant is less than 0.1 parts by weight, the interaction between the metal atom of the carboxylate of the metal atom of the periodic table group 2 and the carbonate portion of the metal carbonate of the periodic table group 2 becomes small and stable. As a result, a liquid overbased metal complex may not be obtained. On the other hand, if the amount is more than 5.0 parts by weight, bubbles may form when preparing a liquid stabilizer using a liquid overbased metal complex, and the workability may be deteriorated.

The liquid overbased metal complex-containing composition according to the present invention is characterized in that the content of the metal atom of Group 2 of the periodic table is high, and thereby, of chlorine-containing resins represented by polyvinyl chloride. It can exhibit excellent effects as a stabilizer.
The content of the metal atom of Group 2 of the periodic table relative to 100% by weight of the liquid overbased metal complex-containing composition is preferably 22 to 41% by weight. More preferably, it is 25 to 38% by weight, still more preferably 28 to 35% by weight. When the content of the metal atom of Group 2 of the periodic table is less than 22% by weight, the effect as a stabilizer of chlorine-containing resin represented by polyvinyl chloride is low, and when it is more than 41% by weight, it is stable as an overbased metal complex It becomes difficult to take a good structure.

<Method of producing liquid overbased metal complex>
The method for producing a liquid overbased metal complex of the present invention comprises a hydroxide of a metal atom of Group 2 of the periodic table, a hydrocarbon solvent having a boiling point of 150 ° C. or more, a monohydric alcohol having 8 to 20 carbon atoms, and a carboxyl group. Group-containing compound and / or phenolic compound, and a first step of forming a carboxylate and / or phenate of the metal atom by mixing a surfactant having a HLB of 10 or more, obtained in the first step Second, adding carbon dioxide to the carboxylate and / or phenate of the metal atom of the periodic table group 2 to form a carboxylate / carbonate complex structure and / or a phenate / carbonate complex structure of the metal atom And in particular, the first step is carried out by mixing HLB 10 or more surfactants.
Thus, by producing using a surfactant having a HLB of 10 or more, the formation of a carbonate precipitate is suppressed to produce a carboxylate / carbonate complex and phenate / carbonate complex of the second group element of the periodic table. Although the reason why it can be done is not clear, it is estimated as follows.
For example, in the case of a carboxylate / carbonate complex of barium, this complex is composed of a complex salt of barium carboxylic acid, barium carbonate and barium carboxylic acid, and is composed mainly of barium carbonate and barium carbonate. A normal carboxylic acid salt and a complex salt of a carboxylic acid of barium and carbonic acid exist in the periphery, and are in a micelle-like state. At the end of the first step, the surfactant having a high HLB containing hydroxyl group and the carboxylate of barium exhibit the function of emulsifying and dispersing, and a nonuniform slurry is obtained together with anhydrous barium hydroxide having a high specific gravity in the reaction system. Form At the time of carbon dioxide gas introduction, it is presumed that a surfactant having a high HLB containing a large amount of hydroxyl groups has a function of stabilizing barium carbonate incorporated into micelles by some kind of interaction.

In the first step, a hydroxide of a metal atom of Group 2 of the periodic table, a monohydric alcohol having 8 to 20 carbon atoms, and a carboxyl group-containing compound and / or a phenol compound are used as raw materials It is a process of producing a carboxylate and / or phenate of a metal atom and a carbonate of a metal atom of Group 2 of the periodic table.

In the first step, a hydroxide of a metal atom of Group 2 of the periodic table, a hydrocarbon solvent having a boiling point of 150 ° C. or higher, a monohydric alcohol having 8 to 20 carbon atoms, a carboxyl group-containing compound and / or a phenol compound And the order of mixing the surfactant having an HLB of 10 or more is not particularly limited, but after mixing the components other than the hydroxide of the metal atom of the periodic table group 2 in advance, the periodic table It is preferable to add and mix the hydroxide of the group metal atom. By mixing in this order, the carboxylic acid positive salt of the metal atom of the periodic table group 2 and the complex salt of the metal atom of the periodic table group 2 with the carboxylic acid are present in a stable state, The reactivity of carbon dioxide with carbon dioxide is stabilized.

The amount of the carboxyl group-containing compound or the phenolic compound used in the first step is preferably 5 to 40 parts by weight with respect to 100 parts by weight of the hydroxide of the metal atom of Group 2 of the periodic table . By using a carboxyl group-containing compound or a phenolic compound at such a ratio, the reactivity with carbon dioxide gas is improved, and a uniform liquid can be easily obtained. More preferably, the amount is 10 to 35 parts by weight, and more preferably 15 to 30 parts by weight with respect to 100 parts by weight of the hydroxide of the metal atom of the periodic table group 2.
When the amount of the carboxyl group-containing compound or the phenolic compound is less than 5 parts by weight, the carbonate may be in a free state, and a uniform liquid may not be obtained. On the other hand, if it is larger than 40 parts by weight, the metal content of the obtained overbased metal complex may be reduced.
When using both a carboxyl group-containing compound and a phenol compound in the first step, it is preferable that the total of the carboxyl group-containing compound and the phenol compound is in the above proportion.

When both a carboxyl group-containing compound and a phenol compound are used in the first step, the molar ratio of the carboxyl group-containing compound and the phenol compound (carboxyl group-containing compound / phenol compound) is 0.5 / 1 to 20 / 1 is preferable. More preferably, it is 1/1 to 10/1, still more preferably 2/1 to 5/1. When the ratio is less than 0.5 / 1, the effect as a stabilizer for chlorine-containing resins such as polyvinyl chloride decreases, and when it is more than 20/1, the reactivity in the first step and the second step is reduced. It often causes a decrease and fails to obtain a uniform liquid.

The amount of monohydric alcohol having 8 to 20 carbon atoms used in the first step is 1.1 to 11.3 parts by weight with respect to 100 parts by weight of a hydroxide of a metal atom of Group 2 of the periodic table Is preferred. By using a monohydric alcohol having 8 to 20 carbon atoms in such a ratio, a carboxylic acid positive salt of a metal atom of the periodic table group 2 and a complex salt of a metal atom of the periodic table group 2 with a carboxylic acid can be obtained. It can exist in a stable state. More preferably, it is 2.6 to 10.2 parts by weight, still more preferably 3.4 to 9.0 parts by weight, with respect to 100 parts by weight of a hydroxide of a metal atom of periodic table group 2 . When the amount of C 8 to C 20 monohydric alcohol is 1.1 parts by weight or less, the carboxylic acid normal salt of metal atom of periodic table group 2 and composite of metal atom of periodic table group 2 metal with carboxylic acid There is a low possibility that the salt can be present in a stable state, and even if it is used at 11.3 parts by weight or more, the reaction promoting effect is small, and the reaction concentration may be reduced to cause a factor that inhibits the reaction.

The amount of the hydrocarbon-based solvent having a boiling point of 150 ° C. or higher used in the first step is preferably 15 to 65 parts by weight with respect to 100 parts by weight of a hydroxide of a metal atom of Group 2 of the periodic table. Using a hydrocarbon solvent at such a ratio allows stable formation of a complex having a carboxylate / carbonate complex structure and / or a phenate / carbonate complex structure formed in the second step in a reverse micelle structure it can. More preferably, it is 25 to 55 parts by weight, and still more preferably 35 to 45 parts by weight with respect to 100 parts by weight of the hydroxide of the metal atom of periodic table group 2. When the amount of the hydrocarbon solvent is less than 15 parts by weight, the viscosity becomes high and the handling as a stabilizer is deteriorated, and when it is more than 65 parts by weight, the metal content becomes low, and chlorine containing resin represented by polyvinyl chloride May be less effective as a stabilizer.

The amount of surfactant having an HLB of 10 or more used in the first step is 0.1 to 5.7 parts by weight with respect to 100 parts by weight of a hydroxide of a metal atom of Group 2 of the periodic table preferable. By using a surfactant having a HLB of 10 or more at such a ratio, the complex of the carboxylate / carbonate complex structure and / or the phenate / carbonate complex structure formed in the second step is stably stabilized in the reverse micelle structure. It can be made to exist. More preferably, it is 0.4 to 3.4 parts by weight, still more preferably 0.6 to 2.3 parts by weight, with respect to 100 parts by weight of the hydroxide of the metal atom of periodic table group 2 . When the amount of the surfactant is less than 0.1 parts by weight, the interaction between the metal atom of the carboxylate or phenate of the metal atom of the periodic table group 2 and the carbonate part of the metal carbonate of the periodic table group 2 becomes small. In some cases, a liquid overbased metal complex can not be obtained stably. On the other hand, if the amount is more than 5.7 parts by weight, bubbles may appear when preparing a liquid stabilizer using a liquid overbased metal complex, and the workability may be deteriorated.

In the first step, a hydroxide of a metal atom of Group 2 of the periodic table, a hydrocarbon solvent having a boiling point of 150 ° C. or higher, a monohydric alcohol having 8 to 20 carbon atoms, a carboxyl group-containing compound and / or a phenol type Hydrocarbon solvent having a boiling point of 150 ° C. or more, carbon number with respect to a hydroxide of a metal atom of Group 2 of the periodic table, as long as a compound and a surfactant having a HLB of 10 or more are mixed Eight to 20 monohydric alcohols, carboxyl group-containing compounds and / or phenolic compounds, and surfactants having an HLB of 10 or more may be added, and conversely, hydrocarbon solvents having a boiling point of 150 ° C. or more, With respect to a mixture of a C8-C20 monohydric alcohol, a carboxyl group-containing compound and / or a phenol compound, and a surfactant having a HLB of 10 or more, a hydroxide of a metal atom of the group 2 of the periodic table Things may be added.

The temperature at which the first step is performed is not particularly limited, but is preferably 50 to 200 ° C. More preferably, it is 60-180 degreeC, More preferably, it is 70-160 degreeC. If the temperature is less than 50 ° C., the reaction becomes extremely slow, and if the temperature is more than 200 ° C., the surfactant is likely to be inactivated, making it difficult to stably obtain a liquid overbased metal complex.

In the first step, a hydroxide of a metal atom of Group 2 of the periodic table, a hydrocarbon solvent having a boiling point of 150 ° C. or higher, a monohydric alcohol having 8 to 20 carbon atoms, a carboxyl group-containing compound and / or a phenol type It is preferable to raise the temperature after mixing the compound and the surfactant having an HLB of 10 or more.
The temperature at the time of mixing is preferably 10 to 100 ° C. More preferably, it is 30 to 90 ° C, and still more preferably 50 to 80 ° C.
Moreover, it is preferable that the temperature after temperature rising shall be 140-170 degreeC. More preferably, it is 145-165 degreeC, More preferably, it is 150-160 degreeC.

The first step is preferably performed under an inert gas atmosphere such as helium, nitrogen, argon or the like. Thereby, in the first step, it is possible to suppress the occurrence of carbonate precipitation.

The time for carrying out the first step is not particularly limited, but is preferably 3 to 9 hours in consideration of the yield of the product and the production efficiency. More preferably, it is 4 to 8 hours, still more preferably 5 to 7 hours.

The first step is preferably carried out while distilling off water generated because of the dehydration reaction.
The first step may be carried out under any of normal pressure, increased pressure and reduced pressure.

Specific examples and preferable atoms of the periodic table group 2 metal atom of the hydroxide of the periodic table group 2 metal atom used in the first step are the same as those in the liquid overbased metal complex composition of the present invention described above. Specific examples and preferred atoms of the periodic table metal group 2 of the periodic table group 2 metal atom carboxylate / carbonate complex structure are the same.

The carboxyl group-containing compound used in the first step is preferably a monovalent carboxylic acid having 8 to 30 carbon atoms. More preferably, it is a C10-C26 monovalent | monohydric carboxylic acid, More preferably, it is a C12-C22 monovalent | monohydric carboxylic acid.
Specific examples and preferable compounds of the carboxyl group-containing compound are the same as the carboxylic acid in the liquid overbased metal complex composition of the present invention described above.

The phenolic compound used in the first step is preferably an alkylphenol having 9 to 30 carbon atoms. More preferably, it is a C10-C26 alkylphenol, More preferably, it is a C12-C20 alkylphenol.
Specific examples and preferable compounds of the phenolic compound are the same as the phenolic compound in the liquid overbased metal complex composition of the present invention described above.

The surfactant having an HLB of 10 or more in the first step may have an HLB of 10 or more, but a surfactant having an HLB of 12 or more is preferable. More preferably, the surfactant has an HLB of 14 or more. If the HLB is less than 10, a carbonate precipitate tends to be produced, making it difficult to stably obtain a liquid overbased metal complex.

Specific examples of the surfactant having an HLB of 10 or more used in the first step are the same as those in the liquid overbased metal complex composition of the present invention described above. Among them, decaglycerin fatty acid ester and / or sorbitan fatty acid ester are preferable. By using decaglycerin fatty acid ester and / or sorbitan fatty acid ester, the complex of the carboxylate / carbonate complex structure and / or the phenate / carbonate complex structure formed in the second step can be further stabilized, The formation of carbonate precipitates in step 2 can be more effectively suppressed.

Specific examples and preferable ones of hydrocarbon solvents having a boiling point of 150 ° C. or higher used in the first step are the same as those in the liquid overbased metal complex composition of the present invention described above.

In the second step, carbon dioxide is added to the carboxylate and / or phenate of the metal atom of Group 2 of the periodic table obtained in the first step to form a carboxylate / carbonate complex structure of the metal atom, and / Alternatively, it is a step of forming a phenate / carbonate complex structure.

The gas used to add carbon dioxide to the carboxylate and / or phenate of the metal atom of Group 2 of the periodic table obtained in the first step may be a gas consisting only of carbon dioxide, It may be a mixed gas containing the following gases.
In the case of a mixed gas, as the other gas, in addition to nitrogen, helium, argon and the like, water vapor and the like can be mentioned, and one containing one or two of these can be used.

The addition amount of carbon dioxide in the second step is 0.3 to 1.3 mol with respect to 1 mol of the hydroxide of the metal atom of Group 2 of the periodic table used as the raw material of the first step preferable. By adding carbon dioxide at such a ratio, a carboxylate / carbonate complex structure and / or a phenate / carbonate complex structure can be sufficiently generated. More preferably, it is 0.5-1.1 mol with respect to 1 mol of hydroxides of the metal atom of periodic table group 2, More preferably, it is 0.7-0.9 mol.
As described above, since the first step is preferably performed under an inert gas atmosphere, the second step is preferably performed by blowing carbon dioxide gas into the reaction solution under the inert gas atmosphere. .

When carbon dioxide is added in the second step, the flow rate of the gas added to the carboxylate and / or phenate of the metal atom of Group 2 of the periodic table obtained in the first step is a gas consisting only of carbon dioxide It may be suitably adjusted according to the gas to be added, such as a mixed gas containing other gases, and in the case of a gas consisting only of carbon dioxide, for example, preferably 10 to 500 ml / min. More preferably, it is 40 to 400 ml / min, still more preferably 70 to 300 ml / min. If the flow rate of gas is too high, the heat of reaction causes the temperature of the solution to rise, which is dangerous.

Although the temperature in particular which performs a 2nd process is not restrict | limited, It is preferable that it is 140-190 degreeC. More preferably, it is 150-180 degreeC, More preferably, it is 160-170 degreeC.
If the temperature is less than 140 ° C., the reaction does not accelerate, and if the temperature exceeds 190 ° C., decomposition tends to occur including the reactants.

The time for carrying out the second step is not particularly limited, but is preferably 2 to 10 hours. More preferably, it is 3 to 9 hours, still more preferably 4 to 8 hours.

The second step may be performed under any of normal pressure, increased pressure and reduced pressure conditions.

In the method for producing a liquid overbased metal complex of the present invention, it is preferable to carry out the step of separating impurities from the product obtained in the second step. The method of separating the impurities is not particularly limited, but filtration is preferred. When performing a filtration process, although you may carry out on any conditions of a normal pressure, pressurization, and pressure reduction, it is preferable to perform pressure filtration. By performing pressure filtration, carbonate contained in the product obtained in the second step can be efficiently removed. The pressure filtration may be performed once or twice or more.

The method for producing a liquid overbased metal complex of the present invention may include other steps other than the first step, the second step, and the step of separating impurities. As another process, the pressure reduction distillation of the water | moisture content which remains in system inside, etc. are mentioned.

The following examples are provided to describe the invention in detail, but the invention is not limited to these examples. Unless otherwise noted, "%" means "wt% (mass%)" and "part" means "part by weight (mass part)", respectively.

Example 1
<First step>
Super oil N-22 (hydrocarbon-based solvent manufactured by JX Energy Co., Ltd.) 88.2 g, Calcol 2098 (C12 alcohol manufactured by Kao Corp.) 9.0 g, nonylphenol 24.0 g (Reagent manufactured by Kanto Chemical Co., Ltd.), PM-810 (Miyoshi fat and oil Oleic acid manufactured by the company: 35.7 g, decaglycerin stearate MSW-7S (surfactant manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) 3.0 g are charged, the temperature is raised while stirring under a nitrogen stream, and barium hydroxide 8 at 60 ° C. The temperature was further raised by charging 238 g of water salt. Since water was distilled off at about 105 ° C., the temperature was raised to 150 ° C. while distilling it off, and finally the pressure was reduced to complete the dehydration reaction.
<Second step>
Subsequently, carbon dioxide gas was blown at a speed of 92 ml / min at 150 to 160 ° C. for 4 hours, and then the pressure was reduced and maintained at 150 ° C. and 60 Torr for 10 minutes.
<Third step>
Thereafter, a nitrogen break was performed to obtain a composition containing a pale yellow liquid overbased carboxylate / carbonate complex (barium content: 34.3%).

Example 2
Overbased in the same manner as the first to third steps of Example 1 except that decaglycerin oleate MO-7S (surfactant manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) was used instead of decaglycerin stearate MSW-7S. The composition containing the basic carboxylate / carbonate complex (barium content 34.3%) was obtained.

Example 3
In the same manner as in the first to third steps of Example 1 except that decaglycerin laurate ML-750 (surfactant manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) was used instead of decaglycerin stearate MSW-7S. A composition containing a basic carboxylate / carbonate complex (barium content 34.3%) was obtained.

Example 4
In the same manner as the first to third steps of Example 1 except that polyoxyethylene sorbitan ester T-80 (surfactant manufactured by Toho Chemical Industry Co., Ltd.) was used instead of decaglycerin stearate MSW-7S. An overbased carboxylate / carbonate complex (barium content 34.3%) containing composition was obtained.

Example 5
In the same manner as the first to third steps of Example 1 except that hexaglycerin laurate ML-500 (surfactant manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) was used instead of decaglycerin stearate MSW-7S. A composition containing a basic carboxylate / carbonate complex (barium content 34.3%) was obtained.

Comparative Example 1
A composition containing an overbased carboxylate / carbonate complex (barium content: 34.5%) in the same manner as in the first to third steps of Example 1 except that the decaglycerin stearate MSW-7S was not used. Obtained.

Comparative example 2
Overbased in the same manner as the first to third steps of Example 1 except that tetraglycerin oleate MO-3S (surfactant manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) was used instead of decaglycerin stearate MSW-7S. The composition containing the basic carboxylate / carbonate complex (barium content 34.3%) was obtained.

Comparative example 3
Overbased in the same manner as the first to third steps of Example 1 except that sorbitan monooleate S-80 (surfactant manufactured by Toho Chemical Industry Co., Ltd.) was used instead of decaglycerin stearate MSW-7S. The composition containing the basic carboxylate / carbonate complex (barium content 34.3%) was obtained.

Physical Properties Evaluation The physical properties of the overbased carboxylate / carbonate complex-containing compositions obtained in Examples 1 to 5 and Comparative Examples 1 to 3 were evaluated by the following methods. The results are shown in Tables 1 and 2.
<Liquefaction degree>
In the second step, when carbonation was carried out, it was visually confirmed whether the complex was a brown liquid. The case where the liquid was brown liquid was 〇, the case where insoluble barium carbonate was deposited on the bottom was バ リ ウ ム, the case where a large amount of barium carbonate was generated and the whole became a white turbid slurry was taken as x.
<Amount of insoluble matter>
Using a pressure filter of φ 15 mm, 5 g of filter aid (Oplite W3050; diatomaceous earth made by Chuo Kasei Co., Ltd.) is spread on quality filter paper (No. 2 made by Toyo Roshi Co., Ltd.) and added under the condition of 2.8 kg / cm ² Pressure filtration was performed to measure the weight of solid content remaining on the filter paper. From the weight of this solid content, the weight of the filter aid (5 g) was subtracted to obtain the weight of insoluble barium carbonate. In addition, the thing with the low degree of liquefaction and which could not measure the amount of insolubles was set to-.
<Filterability>
Measure the time taken to filter the whole amount when performing pressure filtration for insoluble content measurement, measure the filtration time less than 2 minutes ○, 2 minutes or more and less than 5 minutes Δ, 5 minutes or more and less than 10 minutes X, those which could not be totally filtered were regarded as-.

Example 6
<First step>
Super oil N-22 (hydrocarbon solvent manufactured by JX Energy Co., Ltd.) 110.4 g, dodecylphenol 68.6 g (Reagent manufactured by Kanto Chemical Co., Ltd.), PM-810 (oleic acid manufactured by Miyoshi Oil Co., Ltd.) 9.0 g, decaglycerin stear Charge 1.0 g of “rate MSW-7S (Sakamoto Yakuhin Kogyo Co., Ltd. surfactant)”, raise the temperature while stirring under a nitrogen stream, charge 193.6 g of barium hydroxide octahydrate at 60 ° C. and further raise the temperature did. Since water was distilled off at about 105 ° C., the temperature was raised to 150 ° C. while distilling it off, and finally the pressure was reduced to complete the dehydration reaction.
<Second step>
Subsequently, carbon dioxide gas was blown at a speed of 92 ml / min at 150 to 160 ° C. for 4 hours, and then the pressure was reduced and maintained at 150 ° C. and 60 Torr for 10 minutes.
<Third step>
Thereafter, a nitrogen break was performed to obtain a composition containing a pale yellow liquid overbased phenate / carbonate complex (barium content: 28.4%).

Example 7
Overbased in the same manner as the first to third steps of Example 6 except that decaglycerin oleate MO-7S (surfactant manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) was used instead of decaglycerin stearate MSW-7S. An aqueous phenate / carbonate complex (barium content 28.4%) containing composition was obtained.

Example 8
In the same manner as in the first to third steps of Example 6 except that decaglycerin laurate ML-750 (surfactant manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) was used instead of decaglycerin stearate MSW-7S. A composition containing a basic phenate / carbonate complex (barium content 28.4%) was obtained.

Example 9
In the same manner as the first to third steps of Example 6 except using polyoxyethylene sorbitan ester T-80 (surfactant manufactured by Toho Chemical Industry Co., Ltd.) instead of decaglycerin stearate MSW-7S A composition containing overbased phenate / carbonate complex (barium content 28.4%) was obtained.

Example 10
In the same manner as in the first to third steps of Example 6 except that hexaglycerin laurate ML-500 (surfactant manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) was used instead of decaglycerin stearate MSW-7S. A composition containing a basic phenate / carbonate complex (barium content 28.4%) was obtained.

Comparative example 4
An overbased phenate / carbonate complex (barium content: 28.5%)-containing composition was obtained in the same manner as the first to third steps of Example 6 except that the decaglycerin stearate MSW-7S was not used. The

Comparative example 5
Overbased in the same manner as the first to third steps of Example 6 except that tetraglycerin oleate MO-3S (surfactant manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) was used instead of decaglycerin stearate MSW-7S. An aqueous phenate / carbonate complex (barium content 28.4%) containing composition was obtained.

Comparative example 6
Overbased in the same manner as the first to third steps of Example 6 except that sorbitan monooleate S-80 (surfactant manufactured by Toho Chemical Industry Co., Ltd.) was used instead of decaglycerin stearate MSW-7S. An aqueous phenate / carbonate complex (barium content 28.4%) containing composition was obtained.

Physical Property Evaluation The physical properties of the overbased phenate / carbonate complex-containing compositions obtained in Examples 6 to 10 and Comparative Examples 4 to 6 were evaluated by the same method as described above. The results are shown in Tables 3 and 4.

From the results in Tables 1 to 4, in Examples 1 to 10 in which surfactants having an HLB of 10 or more were used, there were few insolubles (precipitates of carbonate) in all, and overbased metals having a good degree of liquefaction A complex was obtained. On the other hand, in Comparative Examples 1 and 4 in which the surfactant was not used, a large amount of barium carbonate was generated, and the composition containing the overbased metal complex did not liquefy. Moreover, in Comparative Examples 2, 3, 5 and 6 using a surfactant having a HLB of less than 10, the amount of insoluble matter is large (Comparative Examples 2 and 5) or a portion in which a large amount of barium carbonate is generated and liquefied. And separation with each other were difficult (Comparative Examples 3 and 6).
From this result, it was confirmed that by producing the liquid overbased metal complex by the production method of the present invention, it is possible to stably produce a high quality liquid overbased metal complex with few insolubles.

Claims (9)

A composition comprising a liquid overbased metal complex having a carboxylate / carbonate complex structure of a metal atom of periodic table group 2 and / or a phenate / carbonate complex structure,
The composition is characterized in that it comprises the liquid perbasic metal complex, a hydrocarbon solvent having a boiling point of 150 ° C. or more, a monohydric alcohol having 8 to 20 carbon atoms, and a surfactant having an HLB of 10 or more. Liquid overbased metal complex-containing composition. The liquid overbased metal complex-containing composition according to claim 1, wherein the metal atom of the periodic table group 2 is at least one selected from the group consisting of calcium, barium, magnesium and strontium. . The liquid overbased metal complex-containing composition according to claim 1 or 2, wherein the carboxylate is formed of a monovalent carboxylic acid having 8 to 30 carbon atoms. The liquid overbased metal complex-containing composition according to any one of claims 1 to 3, wherein the phenate is formed of an alkylphenol having 9 to 30 carbon atoms. The liquid overbased metal complex-containing composition according to any one of claims 1 to 4, wherein the surfactant having a HLB of 10 or more is decaglycerin fatty acid ester and / or sorbitan fatty acid ester. A method for producing a liquid overbased metal complex having a carboxylate / carbonate complex structure of a metal atom of periodic table group 2 and / or a phenate / carbonate complex structure,
The production method comprises a hydroxide of a metal atom of periodic table group 2, a hydrocarbon solvent having a boiling point of 150 ° C. or more, a monohydric alcohol having 8 to 20 carbon atoms, a carboxyl group-containing compound and / or a phenol compound And a first step of mixing a surfactant having a HLB of 10 or more to form a carboxylate and / or a phenate of the metal atom,
A carboxylate / carbonate complex structure of the metal atom and / or a phenate / carbonate complex by adding carbon dioxide to the carboxylate and / or phenate of the metal atom of Group 2 of the periodic table obtained in the first step And a second step of generating a structure. A method of producing a liquid overbased metal complex, comprising: The method for producing a liquid overbased metal complex according to claim 6, wherein the carboxyl group-containing compound is a monovalent carboxylic acid having 8 to 30 carbon atoms. The method for producing a liquid overbased metal complex according to claim 6, wherein the phenolic compound is an alkylphenol having 9 to 30 carbon atoms. The method for producing a liquid overbased metal complex according to any one of claims 6 to 8, wherein the surfactant having an HLB of 10 or more is decaglycerin fatty acid ester and / or sorbitan fatty acid ester.