WO2015199021A1 - Titanium compound and mixture thereof as well as manufacturing methods therefor - Google Patents

Abstract

Provided are: a titanium compound containing a chemical structure represented in formula (1); a mixture with said titanium compound; manufacturing methods therefor; as well as a catalyst using said compound or said mixture. In formula (1), (A) represents a hydrocarbon residue, which is a non-hydroxyl group structural portion of a polyhydric alcohol, (T) represents at least one kind of group selected from a set consisting of dihydric groups represented by formula (2-1) and monohydric groups represented by formula (2-2), and (n) represents an integer of at least 2 that is the same as the valence of hydroxyl groups in the polyhydric alcohol. (a) represents an integer of at least 1, (b) represents an integer of at least 0, and (a) + (b) = (n). In formulas (2-1) and (2-2), L¹, L² and L³ represent 1,3-dicarbonyl compound-derived ligands, aromatic ring-containing monohydric alcohol-derived ligands or monohydric tertiary alcohol-derived ligands.

Description

Titanium compounds and mixtures thereof, and methods for producing them

The present invention relates to a titanium compound that can be suitably used as a catalyst, a mixture thereof, and a production method thereof.

Titanium compounds such as titanium alkoxide compounds and titanium chelate compounds are known to be useful as catalysts for various reactions such as urethanization reactions, esterification reactions, transesterification reactions, and olefin polymerization reactions. Active research and development is being carried out for the purpose of improvement.

For example, International Publication No. 2013/125562 (Patent Document 1) discloses a predetermined titanium compound as a catalyst for promoting a crosslinking reaction of a base resin (reaction between a hydroxyl group or an amino group of the base resin and a block polyisocyanate as a curing agent). It discloses that a coating composition containing (alkoxytitanium condensate) is excellent in curability.

International Publication No. 2012/028637 (Patent Document 2) describes a titanium compound having a glycol-derived moiety and a predetermined hydroxyamine-derived moiety, which is used as a catalyst for urethane bond formation. This titanium compound is said to be excellent in catalytic activity and hydrolysis stability. JP 2013-001812 A (Patent Document 3) describes that a urethanization reactivity in a low temperature region can be improved by using a catalyst composition in which a predetermined hydroxylamine compound is combined with titanium alkoxide. .

International Publication No. 2013/125562 International Publication No. 2012/028637 JP 2013-001812 A

Conventional titanium catalysts have room for improvement in water stability (hydrolysis resistance). For example, when used as a crosslinking catalyst for resins contained in water-based paints, the titanium catalyst hydrolyzes in the paint and precipitates. In some cases, such as causing problems.

Accordingly, an object of the present invention is to provide a novel titanium compound that has good stability to water and can be applied as a reaction catalyst such as a urethanization reaction catalyst.

The present invention provides the following titanium compounds, mixtures of titanium compounds, catalysts, supported catalysts, and methods for producing titanium compounds and mixtures thereof.

[1] The following general formula (1):

[In General Formula (1), A represents a hydrocarbon residue which is a structural portion other than a hydroxyl group in a polyhydric alcohol. T is the following general formula (2-1):

(In the general formula (2-1), L ¹ and L ² are the same or different and are a ligand derived from a 1,3-dicarbonyl compound, a ligand derived from a monohydric alcohol having an aromatic ring, or monovalent. Represents a ligand derived from a tertiary alcohol.)
And a divalent group represented by the following general formula (2-2):

(In the general formula (2-2), L ¹ , L ² and L ³ are the same or different and are a ligand derived from a 1,3-dicarbonyl compound or a ligand derived from a monohydric alcohol having an aromatic ring. Or represents a ligand derived from a monovalent tertiary alcohol.)
And at least one group selected from the group consisting of monovalent groups represented by: a represents an integer of 1 or more, and b represents an integer of 0 or more, provided that a + b = n. n represents an integer of 2 or more which is the same as the valence of the polyhydric alcohol. ]
The titanium compound containing the chemical structure represented by these.

[2] General formula (2-1) below:

(In the general formula (2-1), L ¹ and L ² are the same or different and are a ligand derived from a 1,3-dicarbonyl compound, a ligand derived from a monohydric alcohol having an aromatic ring, or monovalent. Represents a ligand derived from a tertiary alcohol.)
And a divalent group represented by the following general formula (2-2):

(In the general formula (2-2), L ¹ , L ² and L ³ are the same or different and are a ligand derived from a 1,3-dicarbonyl compound or a ligand derived from a monohydric alcohol having an aromatic ring. Or represents a ligand derived from a monovalent tertiary alcohol.)
A group of at least one group T selected from the group consisting of monovalent groups represented by the following is bonded to one hydrocarbon residue A which is a structural part other than a hydroxyl group in an n-valent polyhydric alcohol: Including chemical structure,
A titanium compound in which n is an integer of 2 or more, and a is an integer of 1 to n.

[3] The T includes a divalent group represented by the general formula (2-1), and a is 2 or more.
The titanium compound according to [1] or [2], which contains two or more chemical structures of AT as repeating structural units.

[4] The titanium compound according to any one of [1] to [3], which is represented by the divalent group represented by the general formula (2-1) and the general formula (2-2). A mixture containing two or more types of titanium compounds having different content ratios to monovalent groups.

[5] The mixture according to [4], wherein the two or more types of titanium compounds include a titanium compound in which the T is composed of only a monovalent group represented by the general formula (2-2).

[6] The following general formula (3-1):

[In the general formula (3-1), L ¹ and L ² are the same or different and represent a ligand derived from a 1,3-dicarbonyl compound, a ligand derived from a monohydric alcohol having an aromatic ring, or a monovalent Represents a tertiary alcohol-derived ligand. R ¹ and R ² are the same or different and each represents a monovalent alkyl group. ]
And a titanium complex (a) represented by the following general formula (3-2):

[In the general formula (3-2), L ¹ , L ² and L ³ are the same or different and are a ligand derived from a 1,3-dicarbonyl compound or a ligand derived from a monohydric alcohol having an aromatic ring. Alternatively, it represents a ligand derived from a monovalent tertiary alcohol. R ¹ represents a monovalent alkyl group. ]
Titanium obtained by reaction of at least one titanium complex selected from the group consisting of the titanium complex (b) represented by the formula (1) with an n-valent polyhydric alcohol (n represents an integer of 2 or more). A compound or a mixture containing two or more of the titanium compounds.

[7] The titanium compound or mixture according to [6], wherein the amount of the n-valent polyhydric alcohol used in 1 mole of the titanium complex is in the range of 1.0 / n to 2.4 / n mole.

[8] The titanium compound or mixture according to any one of [1] to [7], wherein n is 6 or less.

[9] A catalyst comprising the titanium compound or mixture according to any one of [1] to [8].
[10] The catalyst according to [9], which is a urethanization reaction catalyst.

[11] A supported catalyst comprising a carrier and the catalyst according to [9] or [10] supported thereon.

[12] The supported catalyst according to [11], wherein the content of the carrier is 3 to 30 parts by mass with respect to 100 parts by mass of the catalyst.

[13] The following general formula (3-1):

[In the general formula (3-1), L ¹ and L ² are the same or different and represent a ligand derived from a 1,3-dicarbonyl compound, a ligand derived from a monohydric alcohol having an aromatic ring, or a monovalent Represents a tertiary alcohol-derived ligand. R ¹ and R ² are the same or different and each represents a monovalent alkyl group. ]
And a titanium complex (a) represented by the following general formula (3-2):

[In the general formula (3-2), L ¹ , L ² and L ³ are the same or different and are a ligand derived from a 1,3-dicarbonyl compound or a ligand derived from a monohydric alcohol having an aromatic ring. Alternatively, it represents a ligand derived from a monovalent tertiary alcohol. R ¹ represents a monovalent alkyl group. ]
A step of reacting at least one titanium complex selected from the group consisting of the titanium complex (b) represented by the formula (1) with an n-valent polyhydric alcohol (n represents an integer of 2 or more) under heating. A method for producing a titanium compound or a mixture containing two or more of the titanium compounds.

[14] The production method according to [13], wherein the amount of the n-valent polyhydric alcohol used per 1 mole of the titanium complex is in the range of 1.0 / n to 2.4 / n mole.

[15] The following general formula (4):

[In General Formula (4), R ¹ , R ² , R ³ and R ⁴ are the same or different and represent a monovalent alkyl group. ]
And at least one ligand compound selected from the group consisting of a 1,3-dicarbonyl compound, a monohydric alcohol having an aromatic ring, and a monovalent tertiary alcohol. The production method according to [13] or [14], further comprising a step of reacting below to obtain the titanium complex.

[16] The production method according to [15], wherein the amount of the ligand compound used relative to 1 mol of the alkoxytitanium compound is in the range of 1.5 to 3.0 mol.

According to the present invention, it is possible to provide a titanium compound and a mixture of titanium compounds that have good water stability and can be applied as a reaction catalyst such as a urethanization reaction catalyst. This titanium compound and mixture of titanium compounds can be suitably used as a curing reaction catalyst for water-based paints as well as solvent-based paints.

It is a schematic diagram which shows partially an example of the chemical structure of the titanium compound which concerns on this invention. It is a schematic diagram which shows partially another example of the chemical structure of the titanium compound which concerns on this invention.

<Titanium compound, mixture of titanium compounds>
The titanium compound according to the present invention is a titanium chelate compound containing Ti (IV), specifically, the following general formula (1):

The chemical structure represented by these is included. In the general formula (1), A represents a hydrocarbon residue which is a structural portion other than a hydroxyl group in a polyhydric alcohol. T is the following general formula (2-1):

And a divalent group represented by the following general formula (2-2):

And at least one group selected from the group consisting of monovalent groups represented by: In general formula (2-1), L ¹ and L ² are the same or different and are a ligand derived from a 1,3-dicarbonyl compound, a ligand derived from a monohydric alcohol having an aromatic ring, or a monovalent Represents a ligand derived from a tertiary alcohol. Similarly, in the general formula (2-2), L ¹ , L ² and L ³ are the same or different and are a ligand derived from a 1,3-dicarbonyl compound or a monohydric alcohol derived from a monohydric alcohol having an aromatic ring. Represents a ligand derived from a ligand or a monovalent tertiary alcohol. In the general formula (1), a representing the number of groups T bonded to the hydrocarbon residue A is an integer of 1 or more, and b representing the number of hydroxyl groups bonded to the hydrocarbon residue A is an integer of 0 or more. Represents. However, a + b = n. n represents an integer of 2 or more that is the same as the valence of the polyhydric alcohol (that is, the valence of the polyhydric alcohol is synonymous).

Thus, the titanium compound according to the present invention contains at least one chemical structure represented by the general formula (1). In other words, in the titanium compound according to the present invention, a number (1 or more and n or less) of the groups T represented by the general formula (2-1) and / or (2-2) is n-valent. It can also be said to be a compound containing at least one chemical structure bonded to one hydrocarbon residue A which is a structural portion other than a hydroxyl group in a polyhydric alcohol.

The titanium compound according to the present invention will be described more specifically. 1 and 2 are schematic views partially showing examples of the chemical structure of the titanium compound according to the present invention. As shown in the figure, the titanium compound according to the present invention has a titanium chelate complex site having a number equal to or less than the valence of the polyhydric alcohol (but 1 or more), that is, the group T is a polyhydric alcohol. It has a structure bonded to a hydrocarbon residue (hydrocarbon residue A). FIG. 1 and FIG. 2 are both examples having a structure in which the same number of titanium chelate complex sites as the valence of the polyhydric alcohol are bonded by the hydrocarbon residue of the polyhydric alcohol. When the polyhydric alcohol is divalent, the titanium compound is linear, but when the polyhydric alcohol is trivalent or higher, it can have a network structure. From the viewpoint of accumulation of titanium atoms, the polyhydric alcohol is preferably trivalent or more, and the number a of the groups T bonded to the hydrocarbon residue A is preferably 2 or more. FIG. 1 is an example using trivalent glycerin as a polyhydric alcohol, and FIG. 2 is an example using tetravalent pentaerythritol. As the ligand compound (chelating agent), benzoylacetone, which is a 1,3-dicarbonyl compound, was used (bzac = benzoylacetonate).

When the group T includes a divalent group represented by the general formula (2-1) as in the titanium compound shown in FIGS. 1 and 2, the titanium compound has a chemical structure represented by AT. In the network structure constructed by polyhydric alcohol as shown in FIGS. 1 and 2 (particularly the group represented by the general formula (2-1)). ) Is more preferable. When the titanium compound contains two or more chemical structures of AT as repeating structural units, a is 2 or more.

In the case where the titanium compound contains two or more chemical structures of AT as repeating structural units, one oxygen atom (O) in the divalent group represented by the general formula (2-1) is The other oxygen atom (O) in the divalent group represented by the general formula (2-1) is bonded to another A different from this.

1 and 2 show an example in which the group T is composed of only a divalent group represented by the general formula (2-1). However, the present invention is not limited to this, and a titanium compound is generally used as the group T. It may have both a divalent group represented by the formula (2-1) and a monovalent group represented by the general formula (2-2), or the group T may have the general formula (2- You may have only the monovalent group represented by 2). In the titanium compound of the present invention, it is not always necessary that all the hydroxyl groups of the polyhydric alcohol are substituted with the group T, and some of the hydroxyl groups possessed by the polyhydric alcohol may remain.

The present invention also provides a mixture of titanium compounds containing two or more of the above titanium compounds. The mixture is a mixture of two or more titanium compounds having different content ratios of the divalent group represented by the general formula (2-1) and the monovalent group represented by the general formula (2-2). Can be mentioned. An example of such a mixture is a titanium compound containing a divalent group represented by the general formula (2-1) as the group T and a monovalent group wherein the group T is represented by the general formula (2-2). It is a mixture with the titanium compound which consists only of. Other examples of the mixture include a combination of titanium compounds having the same n but different b values (and hence a value), a combination of titanium compounds having different n, and a combination of titanium compounds having different A. it can.

Specifically, a titanium compound in which the group T is composed of only a monovalent group represented by the general formula (2-2) is represented by the following formula (1a):
A- [O-Ti (L ¹ L ² L ³ )] _n (1a)
Or (HO) _b -A- [O-Ti (L ¹ L ² L ³ )] _a (1b)
Compared with a highly integrated titanium compound having a network structure as shown in FIGS. 1 and 2, it is a titanium compound having a relatively low molecular weight. In the formula (1b), b is an integer of 1 or more, a is an integer of 1 or more, and a + b = n.

The titanium compound of the present invention and a mixture thereof are more advantageous than conventional titanium catalysts in that both catalytic activity and water stability can be achieved. The titanium compound of the present invention and the mixture thereof show good catalytic activity, and particularly show excellent catalytic activity when a titanium compound having two or more groups T is contained. This excellent catalytic activity is considered to be due to the ability to accumulate titanium atoms efficiently by crosslinking of hydrocarbon residues A. Further, the titanium compound and the mixture thereof of the present invention have good stability to water (including moisture in the air, moisture contained in, for example, paints, and water as a solvent). Stability is due to the protective effect of titanium atoms (stabilization of titanium atoms) by the bridge structure (hydrocarbon residue A) having a ligand (L ¹ , L ² , L ³ ) and a hydrocarbon skeleton. Presumed. For example, when the titanium compound of the present invention or a mixture thereof is used as a curing catalyst for a coating resin (such as a urethanization reaction catalyst), the coating material containing the titanium compound or a mixture thereof has both storage stability and curability. Thus, it is possible to form a coating film having excellent durability and weather resistance. The titanium compounds and mixtures thereof of the present invention are particularly useful as curing catalysts for water-based paints.

When the titanium compound has both a divalent group represented by the general formula (2-1) and a monovalent group represented by the general formula (2-2) as the group T, By adjusting the content ratio of these groups, the balance between the catalytic activity and stability of the titanium compound can be controlled. That is, as the content ratio of the monovalent group represented by the general formula (2-2) is increased, more molecular ends are formed, so that the condensation degree (molecular weight) of the titanium compound can be reduced. By increasing the content ratio of the valent group, the characteristics of the titanium compound tend to be shifted in the direction of high catalytic activity and low stability. On the other hand, by reducing the content ratio of the monovalent group, the characteristics of the titanium compound tend to be shifted in the direction of low catalytic activity and high stability.

Similarly, by adjusting the content ratio of two or more kinds of titanium compounds to be mixed, it is possible to control the balance between the catalytic activity and the stability of the mixture of titanium compounds.

The polyhydric alcohol forming the hydrocarbon residue A is a dihydric or higher alcohol, and specific examples thereof are ethylene glycol, propylene glycol, trimethylpentanediol, dimethylpropanediol, methylpropanediol, butylethylpropanediol, neopentyl. Dihydric alcohols such as glycol, hexylene glycol, cyclohexanedimethanol and hydrogenated bisphenol A; trihydric alcohols such as glycerin and trimethylolpropane; tetrahydric alcohols such as erythritol, pentaerythritol, ditrimethylolpropane and orthocarbonic acid; Contains a hexahydric alcohol such as dipentaerythritol. Of course, alcohols having a valence of 7 or more may be used. In addition to these, saccharides; polyols obtained from resin synthesis; polycaprolactone diols; polycarbonate diols; alkoxylated polyhydric alcohols (for example, “Voxtar”, “Polyol”, “Capa”, “Boltorn” manufactured by Perstorp) , “Oxymer”, etc.) can also be used as the polyhydric alcohol. Only 1 type may be used for a polyhydric alcohol and it may use 2 or more types together. The valence of the polyhydric alcohol, that is, n is preferably 6 or less.

Depending on the chemical structure of the polyhydric alcohol, the hydrocarbon residue A may contain atoms other than C atoms and H atoms (N atoms, halogen atoms, etc.).

The divalent group represented by the general formula (2-1) and the monovalent group represented by the general formula (2-2) are each represented by the following general formula (3-1):

A titanium complex (a) represented by the following general formula (3-2):

It can be a group derived from a titanium complex (b) represented by: L ¹ and L ² in the general formula (3-1) is the general formula (2-1) the same meaning as L ¹ and L ² of, R ¹ and R ² are the same or different monovalent alkyl Represents a group. A general formula (3-2) L ^1, L ² and L ³ are the same meaning as the general formula (2-2) L ^1, L ² and L ³ in the in the R ¹ is a monovalent alkyl radical To express. The titanium complexes represented by the general formulas (3-1) and (3-2) can be produced from the corresponding titanium source compound.

A typical example of the corresponding titanium source compound is the following general formula (4):

It is the alkoxy titanium compound (tetraalkoxy titanium compound) represented by these. In the general formula (4), R ¹ , R ² , R ³ and R ⁴ are the same or different and represent a monovalent alkyl group.

Specific examples of R ¹ , R ² , R ³ and R ^{4 in} the general formulas (3-1), (3-2) and (4) are methyl group, ethyl group, n- or i-propyl group, n- I- or t-butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, 2-ethylhexyl group. An alkyl group having 3 or less carbon atoms is preferred.

Specific examples of the alkoxy titanium compound represented by the general formula (4) include tetramethoxy titanium, tetraethoxy titanium, tetra n-propoxy titanium, tetraisopropoxy titanium (titanium isopropoxide), tetrabutoxy titanium (titanium butoxide), Contains tetrakis (2-ethylhexyloxy) titanium.

Also, as the titanium source compound, a multimer of the above alkoxytitanium compounds, for example, tetrabutoxytitanium dimer, tetrabutoxytitanium tetramer, tetrabutoxytitanium heptamer, tetrabutoxytitanium decamer, and the like can be used. Multimers of alkoxytitanium compounds can also be obtained as commercial products such as those manufactured by Nippon Soda. A titanium source compound may use only 1 type and may use 2 or more types together.

The 1,3-dicarbonyl compounds forming the ligands represented by L ¹ , L ² and L ³ in the general formulas (2-1) and (2-2) are represented by the following general formula (5):

It can be the compound represented by these. In this case, L ¹ , L ² and L ³ are represented by the following general formula (6) or (7):

It is represented by In the general formulas (5), (6) and (7), R ⁵ and R ⁶ are the same or different and each represents a monovalent hydrocarbon group, an alkoxy group or a primary or secondary amino group. Specific examples of the monovalent hydrocarbon group include a methyl group, an ethyl group, an n- or i-propyl group, an n-, i- or t-butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, and an octyl group. , Saturated hydrocarbon groups such as dodecanyl group and octadecanyl group; unsaturated hydrocarbon groups such as vinyl group, allyl group, cyclopentadienyl group, aryl group (phenyl group, benzyl group, etc.). A saturated or unsaturated hydrocarbon group having 1 to 12 carbon atoms is preferred.

Specific examples of alkoxy groups include methoxy, ethoxy, n- or i-propoxy, n-, i- or t-butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy , Nonyloxy group, decanyloxy group, dodecanyloxy group and phenoxy group. An alkoxy group having 1 to 12 carbon atoms is preferable.

Specific examples of the primary or secondary amino group include dimethylamino group, diethylamino group, diisopropylamino group, phenylamino group, methylphenylamino group, ethylphenylamino group, and arylamino group. A secondary amino group having 1 to 12 carbon atoms is preferred.

In the general formulas (5), (6), and (7), R ⁷ represents a hydrogen atom or a monovalent hydrocarbon group. Specific examples of the monovalent hydrocarbon group include a methyl group, an ethyl group, an n- or i-propyl group, an n-, i- or t-butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, and an octyl group. Saturated hydrocarbon groups such as 2-ethylhexyl group; unsaturated hydrocarbon groups such as vinyl group, allyl group, cyclopentadienyl group, aryl group (phenyl group, benzyl group, etc.). A hydrogen atom or a saturated or unsaturated hydrocarbon group having 1 to 12 carbon atoms is preferred.

Specific examples of the 1,3-dicarbonyl compound represented by the general formula (5) include 2,4-pentanedione (acetylacetone), 2,4-hexanedione, 2,4-pentadecanedione, 2,2, 6,6-tetramethyl-3,5-heptanedione, 5,5-dimethyl-2,4-hexanedione, 1-cyclohexyl-1,3-butanedione, 1-phenyl-1,3-butanedione (benzoylacetone) 1-aryl-1,3-butanedione such as 1- (4-methoxyphenyl) -1,3-butanedione; 1,3-diphenyl-1,3-propanedione, 1,3-bis (2-pyridyl) ) -1,3-propanedione, 1,3-diaryl-1,3-propanedione such as 1,3-bis (4-methoxyphenyl) -1,3-propanedione; Including the diketones such as; Njiru-2,4-pentanedione.

Other specific examples of 1,3-dicarbonyl compounds include methyl acetoacetate, ethyl acetoacetate, butyl acetoacetate, t-butyl acetoacetate, benzyl acetoacetate (benzyl acetoacetate), and ethyl 3-oxohexanoate. Ketoesters; ketoamides such as N, N-dimethylacetoacetamide, N, N-diethylacetoacetamide and acetoacetanilide; malonic acid esters such as dimethylmalonate, diethylmalonate and diphenylmalonate Malonic acid amides such as N, N, N ′, N′-tetramethylmalonamide, N, N, N ′, N′-tetraethylmalonamide; Only one type of 1,3-dicarbonyl compound may be used, or two or more types may be used in combination.

Examples of the monohydric alcohol having an aromatic ring that forms a ligand represented by L ¹ , L ² , or L ³ in the general formulas (2-1) and (2-2) include benzyl alcohol, cumyl Contains phenolic hydroxyl groups in addition to alcohol, cinnamyl alcohol, diphenylmethanol, triphenylmethanol, 9-hydroxymethyl-anthracene, benzoin, 1-hydroxy-cyclohexyl-phenylketone, 2-hydroxy-2-methylpropiophenone, etc. Examples include phenol, cresol, naphthol, dibutylhydroxytoluene, methyl salicylate, anthracenol and the like.

The monovalent tertiary alcohol that forms the ligand represented by L ¹ , L ² , or L ³ in the above general formulas (2-1) and (2-2) is 2-methyl-2-propanol. (T-butanol), 2-ethyl-2-propanol, 2-ethyl-2-butanol, 3-ethyl-3-pentanol, 2-phenyl-2-propanol, 1,1-diphenylethanol, 1,1, Examples thereof include 1-triphenylmethanol.

Monohydric alcohol can be used in combination with polyhydric alcohol. In this case, the titanium compound has the following general formula (2 '):

In [Formula (2 '), L ¹ and L ² in formula (2-1) L ¹ and L ² the same meaning in the. Z represents a hydrocarbon residue which is a structural portion other than a hydroxyl group in a monohydric alcohol. ]
As such, the molecular chain may include a structural portion terminated with a hydrocarbon residue Z. By using a monohydric alcohol in combination as necessary, the degree of condensation (molecular weight) of the titanium compound can be controlled, whereby the balance between the catalytic activity and stability of the titanium compound can be controlled.

Specific examples of the monohydric alcohol include ethanol, n- or i-propanol, n-, i- or t-butanol, n-hexanol, 2-ethylhexanol, benzyl alcohol, cumyl alcohol, cinnamyl alcohol, diphenylmethanol, Triphenylmethanol, 9-hydroxymethyl-anthracene, benzoin, 1-hydroxy-cyclohexyl-phenyl ketone, 2-hydroxy-2-methylpropiophenone, ethyl cellosolve, butyl cellosolve, hexyl cellosolve, 2-ethylhexyl cellosolve, butyldi Glycol (diethylene glycol monobutyl ether), propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, 2-ethyl Including sill diglycol, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether, glycol ethers such as 1-phenoxy-2-propanol (phenyl propylene glycol). As for monohydric alcohol, only 1 type may be used and 2 or more types may be used together. The monohydric alcohol used here is preferably a monohydric alcohol that can substitute the —OR ¹ group or the —OR ² group in the general formula (3-1).

Note that, as described above, the titanium compound of the present invention and the titanium compound contained in the mixture may include a structural portion in which the molecular chain is stopped by remaining unreacted hydroxyl groups of the polyhydric alcohol. In addition, the titanium compound of the present invention and the titanium compound contained in the mixture are a divalent group represented by the general formula (2-1) and / or a monovalent group represented by the general formula (2-2). In addition to the group, the following formula (2-3):

The trivalent group represented by these may be included.
<Method for producing titanium compound and mixture thereof>
The titanium compound is at least one selected from the group consisting of the titanium complex (a) represented by the general formula (3-1) and the titanium complex (b) represented by the general formula (3-2). It can be obtained by reacting a titanium complex with the polyhydric alcohol. As described above, a monohydric alcohol can be used in combination with a polyhydric alcohol for the purpose of adjusting the degree of condensation (molecular weight) of the titanium compound. Each of the titanium complex, polyhydric alcohol and monohydric alcohol may be used alone or in combination of two or more. The reaction is preferably performed under heating.

When only the titanium complex (a) is used as the titanium complex, a titanium compound in which the group T is composed only of a divalent group represented by the general formula (2-1) is usually obtained. When only the titanium complex (b) is used as the titanium complex, the above titanium compound (1a) or (1b) is usually obtained in which the group T consists only of a monovalent group represented by the general formula (2-2). It is done. By using both of the titanium complexes (a) and (b), the group T is a divalent group represented by the general formula (2-1) and a monovalent group represented by the general formula (2-2). A titanium compound containing both of the above, or two or more kinds of divalent groups represented by the general formula (2-1) and the monovalent group represented by the general formula (2-2) are different from each other. A mixture of titanium compounds can be obtained. Further, the mixture includes a titanium compound obtained using a titanium complex having a titanium complex (a) / titanium complex (b) ratio of X, and a titanium complex (a) / titanium complex (b) ratio of Y (X and Can be obtained by mixing later with a titanium compound obtained using a titanium complex having a different value.

The amount of polyhydric alcohol used per mole of titanium complex can be in the range of 1.0 / n to 2.4 / n mole (where n is the valence of the polyhydric alcohol), preferably 1 It is in the range of .6 / n to 2.3 / n mol, more preferably 1.8 / n to 2.2 / n mol. If either one of the titanium complex and the polyhydric alcohol is used in an excessive amount, the chemical structure represented by the general formula (1) is hardly formed, or the polyhydric alcohol is stoichiometrically compared to the titanium complex. If the amount is excessive, part of the hydroxyl groups of the polyhydric alcohol tends to remain. In the case where both of the titanium complexes (a) and (b) are used as the titanium complex, the degree of condensation (molecular weight) of the titanium compound obtained by adjusting the use ratio thereof can be controlled, and the titanium compound In the mixture, the content ratio of each titanium unit contained in the mixture can be controlled.

The reaction temperature is not particularly limited and can be, for example, about 100 to 250 ° C. The reaction is preferably performed in the presence of an organic solvent. In order to promote the reaction, it is preferable to exclude from the reaction system alcohols (R ¹ OH and R ² OH) derived from titanium complexes that are by-produced during the reaction. The organic solvent is not particularly limited as long as it does not inhibit the reaction.

The titanium catalyst which is the titanium complex (a) represented by the general formula (3-1) and / or the titanium complex (b) represented by the general formula (3-2) is represented by the general formula (4). And a 1,3-dicarbonyl compound represented by the above general formula (5), a monohydric alcohol having an aromatic ring, and a monovalent tertiary alcohol. It can be obtained by reacting with at least one selected ligand compound. Only 1 type may be used for an alkoxy titanium compound, another titanium source compound, and a ligand compound, respectively, and 2 or more types may be used together. The reaction is preferably performed under heating.

The amount of the ligand compound used per mole of the alkoxytitanium compound is in the range of 1.5 to 3.0 moles. If the amount of either an alkoxytitanium compound or a ligand compound used is excessively large, a titanium complex of the general formula (3-1) having two ligand-derived ligands in the molecule is formed. In other words, the production amount of the titanium complex (b) represented by the general formula (3-2) can be increased by increasing the amount of the ligand compound used. When an m-mer of an alkoxytitanium compound (m is an integer of 2 or more) is used as the titanium source compound, the m-mer is equivalent to 1 mol of an alkoxytitanium compound.

The reaction temperature is not particularly limited and can be, for example, about 50 to 200 ° C. The reaction is preferably performed in the presence of an organic solvent. In order to promote the reaction, it is preferable to exclude from the reaction system alcohols (R ² OH, R ³ OH, R ⁴ OH) derived from titanium source compounds that are by-produced during the reaction. The organic solvent is not particularly limited as long as it does not inhibit the reaction.

As another method for producing a titanium compound, a method of reacting a titanium source compound (such as an alkoxytitanium compound), a ligand compound and a polyhydric alcohol in one step (one pot) can be mentioned. However, from the viewpoint of suppressing by-products, it is preferable to perform the reaction sequentially (in two stages) as described above.

<Titanium compound, catalyst application of titanium compound mixture>
As described above, the titanium compound and the mixture of the present invention can be suitably used as a reaction catalyst. The titanium compound and the mixture can be a reaction catalyst such as a urethanization reaction, a reaction between an isocyanate and an epoxy group, an esterification reaction, a transesterification reaction, an olefin polymerization reaction, etc., among which are suitable as a urethanization reaction catalyst, Good catalytic activity.

Urethane reaction is a reaction between an isocyanate component and a polyol component. Specific examples of the isocyanate component include an organic polyisocyanate or a dimer, a trimer, a burette, and a blocked isocyanate, as well as a urethane prepolymer. Specific examples of the polyol component include polyether polyol, polyester polyol, polycarbonate polyol, acrylic polyol, polybutadiene polyol, polyurethane polyol, and epoxy polyol.

As described above, since the titanium compound and the mixture of the present invention have good stability to water, they are particularly suitable for applications that take advantage of such advantages. Examples of such applications include paint applications, that is, curing catalysts for paint resins. For example, the titanium compound or mixture of the present invention can be suitably applied to an aqueous coating composition using a urethane curing system. In addition, since the stability to water is good, the titanium compound and the mixture of the present invention can enhance the storage stability of the paint regardless of whether the paint is solvent-based or aqueous. The titanium compound and the mixture of the present invention can themselves be excellent in storage stability in air, for example.

The titanium compound and the mixture of the present invention can be used as they are for the catalyst application as described above, but those supported on a carrier may be used as a catalyst. By using a supported catalyst, the catalyst activity and / or stability tends to be improved. The carrier can be, for example, granular, granular, powdery and the like.

Specific examples of the material constituting the carrier include, for example, silica, clay, kaolinite, kaolin, synthetic hydrotalcite, talc, carbon black, graphite, bengara (valve), inorganic substances such as metal compounds, cellulose, Organic substances such as cellulose acetate and other thermoplastic resins.

Examples of the metal constituting the metal compound include magnesium, aluminum, calcium, barium, iron, palladium, titanium, platinum, copper, zinc, lead, bismuth, ruthenium, tin, and one or more metals Can be included. Specific examples of the metal compound include metal oxides such as titanium oxide, zinc oxide, iron oxide, aluminum oxide, magnesium oxide, bismuth oxide and tin oxide; magnesium acetate, magnesium lactate, calcium acetate, tris (2-ethylhexanoic acid) ) Metals such as iron (III), copper acetate, copper lactate, copper benzoate, zinc acetate, zinc lactate, zinc dimethylolpropionate, zinc benzoate, bismuth acetate, bismuth succinate, bismuth lactate, aluminum polyphosphate Organic acids or phosphates; metal sulfates such as barium sulfate and lead sulfate; metal hydroxides such as aluminum hydroxide and bismuth hydroxide; bis (2,4-pentadionato) magnesium (II), tris ( 2,4-pentadionato) aluminum (III), tris (2,4-pentadionato) iron (I I), tris (1,3-diphenyl-1,3-propanedionato) iron (III), bis (2,4-pentadionato) copper (II), bis (2,4-pentadionato) zinc (II), Chelate complexes such as tris (2,4-pentadionato) bismuth (III) are included.

Only one type of carrier may be used, or two or more types may be used in combination. In the supported catalyst, the content of the carrier with respect to 100 parts by mass of the catalyst which is a titanium compound or a mixture can be 3 to 30 parts by mass, preferably 2 to 25 parts by mass, more preferably 5 to 20 parts by mass. is there.

Although the manufacturing method of a supported catalyst is not specifically limited, For example, the following method is mentioned.
a) a method in which the reaction between the titanium complex and the polyhydric alcohol is carried out in the presence of a carrier, and the resulting titanium compound is supported on the carrier;
b) The reaction between the titanium source compound and the ligand compound is carried out in the presence of the carrier, and the produced titanium complex is supported on the carrier, and then the supported titanium complex is reacted with the polyhydric alcohol, A method for obtaining a supported catalyst in which a titanium compound is supported on a carrier;
c) A method of obtaining a supported catalyst in which a titanium compound is supported on a support by performing a one-step reaction of a titanium source compound, a ligand compound and a polyhydric alcohol in the presence of a support,
d) A method in which a titanium compound is prepared and then supported on a carrier by dipping, adsorption or the like.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples.

<Example 1>
[1] Preparation of Titanium Complex A reaction vessel equipped with a stirrer, a reflux condenser with a Dean-Stark device, a temperature controller, and a nitrogen introduction tube was purged with nitrogen, and then 100 parts by mass of tetraisopropoxy titanium (IV) was added, and nitrogen was added. Stir in a stream of air. Next, 114.3 parts by mass of benzoylacetone as a ligand compound (1,3-dicarbonyl compound) and 50 parts by mass of heptane as a reaction solvent were added, and the temperature was raised to 120 ° C. over 1 hour with stirring. did. During this temperature increase, about 43 parts by mass of isopropyl alcohol as a by-product was removed from the system by a nitrogen stream using a Dean Stark apparatus. It cooled to 40 degreeC and the reaction liquid containing the benzoyl acetonato titanium complex which is a titanium complex was obtained. From the amount of isopropyl alcohol recovered, it was confirmed that an average of 2 moles of benzoylacetonate ligand was coordinated per mole of tetraisopropoxytitanium (IV).

[2] Preparation of titanium compound 10 parts by weight of kaolin (“Siritin Z86” manufactured by Hoffman Mineral Co., Ltd.) as a carrier and 21.4 parts by weight of glycerin, which is a polyhydric alcohol, are added to the above reaction mixture and mixed and stirred. The temperature was raised to 180 ° C. over 1 hour, and the temperature was kept at the same temperature for 1 hour. Subsequently, it heated up to 210 degreeC over 1 hour, mixing and stirring. During this time, in order to complete the ligand exchange reaction of the titanium complex, about 43 parts by mass of isopropyl alcohol by-produced was excluded from the system using a Dean-Stark apparatus. Subsequently, after cooling to 40 degreeC, it filtered and wash | cleaned, and it was made to dry and the brown powdery titanium compound was obtained. From the amount of isopropyl alcohol recovered, it was confirmed that the isopropoxy group of the titanium complex was almost quantitatively substituted with the hydroxyl group of glycerin.

<Examples 2 to 30>
A titanium compound was prepared in the same manner as in Example 1 except that the type and amount of the raw material were changed as shown in Table 1. The numerical value of each raw material in Table 1 indicates parts by mass.

<Comparative Example 1>
A titanium compound was prepared in the same manner as in Example 1 except that benzoylacetone was not used.

<Comparative example 2>
A titanium compound was prepared in the same manner as in Example 1 except that glycerin was not used.

<Evaluation of titanium compounds>
[1] Evaluation of hydrolysis resistance A screw tube was filled with 1 g of a titanium compound, 10 g of deionized water, and a stirrer chip. The contents were stirred for 32 hours at 25 ° C. using a magnetic stirrer, and the insoluble matter was filtered using a filter paper (ADVANTEC TOYO 5C, 125 mm). The filter cake was dried together with the filter paper (80 to 90 ° C., 1 hour), and the mass of the insoluble matter was measured. Following formula:
Insoluble content rate (%) = 100 × mass insoluble content g / 1 g
Based on the above, the insoluble fraction was determined, and the hydrolysis resistance was evaluated according to the following evaluation criteria. A score of 4 or more was accepted. The evaluation results are shown in Table 1.

5 points: 95% or more insoluble content,
4 points: 90% or more insoluble content,
3 points: 80% or more insoluble content,
2 points: Insoluble fraction is less than 80%.

[2] Evaluation of catalytic activity 9 g of acrylic polyol (“Acridick A-801” manufactured by DIC Corporation, solid content 50 mass%) was added to 9 g of blocked isocyanate (“Duranate TPA-B80” manufactured by Asahi Kasei Chemicals Corporation, solid content 80 (Mass%) 1 g was mixed to prepare 10 g of urethane-curing coating resin.

Separately, the titanium compound was weighed by 3% by mass of the resin solids for paint and diluted with a solvent (THF). 10 g of the above resin for paint was added to this diluted solution and stirred well to obtain a paint. Next, this paint was applied to a tin plate and baked under conditions of 160 ° C. × 15 minutes to form a dry coating film. Next, the tin plate having this coating film was immersed in acetone (25 ° C.) for 24 hours, and then dried under conditions of 110 ° C. × 20 minutes, and the mass of the coating film after drying was measured. Following formula:
Gel fraction (%) = 100 × (film mass g after acetone immersion / drying) / (mass g of dry film before acetone immersion)
The gel fraction was determined based on the above, and the catalytic activity was evaluated according to the following evaluation criteria. A score of 4 or more was accepted. The evaluation results are shown in Table 1.

5 points: gel fraction 95% or more,
4 points: gel fraction 90% or more,
3 points: Gel fraction 80% or more,
2 points: Gel fraction less than 80%.

Claims (16)

The following general formula (1):

[In General Formula (1), A represents a hydrocarbon residue which is a structural portion other than a hydroxyl group in a polyhydric alcohol. T is the following general formula (2-1):

(In the general formula (2-1), L ¹ and L ² are the same or different and are a ligand derived from a 1,3-dicarbonyl compound, a ligand derived from a monohydric alcohol having an aromatic ring, or monovalent. Represents a ligand derived from a tertiary alcohol.)
And a divalent group represented by the following general formula (2-2):

(In the general formula (2-2), L ¹ , L ² and L ³ are the same or different and are a ligand derived from a 1,3-dicarbonyl compound or a ligand derived from a monohydric alcohol having an aromatic ring. Or represents a ligand derived from a monovalent tertiary alcohol.)
And at least one group selected from the group consisting of monovalent groups represented by: a represents an integer of 1 or more, and b represents an integer of 0 or more, provided that a + b = n. n represents an integer of 2 or more which is the same as the valence of the polyhydric alcohol. ]
The titanium compound containing the chemical structure represented by these. The following general formula (2-1):

(In the general formula (2-1), L ¹ and L ² are the same or different and are a ligand derived from a 1,3-dicarbonyl compound, a ligand derived from a monohydric alcohol having an aromatic ring, or monovalent. Represents a ligand derived from a tertiary alcohol.)
And a divalent group represented by the following general formula (2-2):

(In the general formula (2-2), L ¹ , L ² and L ³ are the same or different and are a ligand derived from a 1,3-dicarbonyl compound or a ligand derived from a monohydric alcohol having an aromatic ring. Or represents a ligand derived from a monovalent tertiary alcohol.)
A group of at least one group T selected from the group consisting of monovalent groups represented by the following is bonded to one hydrocarbon residue A which is a structural part other than a hydroxyl group in an n-valent polyhydric alcohol: Including chemical structure,
A titanium compound in which n is an integer of 2 or more, and a is an integer of 1 to n. T includes a divalent group represented by the general formula (2-1), a is 2 or more,
The titanium compound according to claim 1 or 2, which contains two or more chemical structures of AT as repeating structural units. The titanium compound according to any one of claims 1 to 3, wherein the divalent group represented by the general formula (2-1) and the monovalent group represented by the general formula (2-2) The mixture containing 2 or more types of titanium compounds from which content ratio with group of mutually differs. The mixture according to claim 4, wherein the two or more kinds of titanium compounds include a titanium compound in which the T is composed only of a monovalent group represented by the general formula (2-2). The following general formula (3-1):

[In the general formula (3-1), L ¹ and L ² are the same or different and represent a ligand derived from a 1,3-dicarbonyl compound, a ligand derived from a monohydric alcohol having an aromatic ring, or a monovalent Represents a tertiary alcohol-derived ligand. R ¹ and R ² are the same or different and each represents a monovalent alkyl group. ]
And a titanium complex (a) represented by the following general formula (3-2):

[In the general formula (3-2), L ¹ , L ² and L ³ are the same or different and are a ligand derived from a 1,3-dicarbonyl compound or a ligand derived from a monohydric alcohol having an aromatic ring. Alternatively, it represents a ligand derived from a monovalent tertiary alcohol. R ¹ represents a monovalent alkyl group. ]
Titanium obtained by reaction of at least one titanium complex selected from the group consisting of the titanium complex (b) represented by the formula (1) with an n-valent polyhydric alcohol (n represents an integer of 2 or more). A compound or a mixture containing two or more of the titanium compounds. The titanium compound or mixture according to claim 6, wherein the amount of the n-valent polyhydric alcohol used per mole of the titanium complex is in the range of 1.0 / n to 2.4 / n mole. The titanium compound or mixture according to any one of claims 1 to 7, wherein n is 6 or less. A catalyst comprising the titanium compound or mixture according to any one of claims 1 to 8. The catalyst according to claim 9, which is a urethanization reaction catalyst. A supported catalyst comprising a carrier and the catalyst according to claim 9 or 10 supported thereon. The supported catalyst according to claim 11, wherein the content of the carrier is 3 to 30 parts by mass with respect to 100 parts by mass of the catalyst. The following general formula (3-1):

[In the general formula (3-1), L ¹ and L ² are the same or different and represent a ligand derived from a 1,3-dicarbonyl compound, a ligand derived from a monohydric alcohol having an aromatic ring, or a monovalent Represents a tertiary alcohol-derived ligand. R ¹ and R ² are the same or different and each represents a monovalent alkyl group. ]
And a titanium complex (a) represented by the following general formula (3-2):

[In the general formula (3-2), L ¹ , L ² and L ³ are the same or different and are a ligand derived from a 1,3-dicarbonyl compound or a ligand derived from a monohydric alcohol having an aromatic ring. Alternatively, it represents a ligand derived from a monovalent tertiary alcohol. R ¹ represents a monovalent alkyl group. ]
A step of reacting at least one titanium complex selected from the group consisting of the titanium complex (b) represented by the formula (1) with an n-valent polyhydric alcohol (n represents an integer of 2 or more) under heating. A method for producing a titanium compound or a mixture containing two or more of the titanium compounds. The production method according to claim 13, wherein the amount of the n-valent polyhydric alcohol used in 1 mol of the titanium complex is in the range of 1.0 / n to 2.4 / n mol. The following general formula (4):

[In General Formula (4), R ¹ , R ² , R ³ and R ⁴ are the same or different and represent a monovalent alkyl group. ]
And at least one ligand compound selected from the group consisting of a 1,3-dicarbonyl compound, a monohydric alcohol having an aromatic ring, and a monovalent tertiary alcohol. The manufacturing method of Claim 13 or 14 which further includes the process of making it react below and obtaining the said titanium complex. The production method according to claim 15, wherein the amount of the ligand compound used relative to 1 mol of the alkoxytitanium compound is in the range of 1.5 to 3.0 mol.

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