JPH0160510B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to compositions for dissolving polymetalloxanes. Polymetalloxanes, for example, have the general formula

【formula】

[Formula] (In the formula, M ₁ is a tetravalent metal, M ₂ is a trivalent metal,
A polymer having a structural unit (Y ₁ and Y ₂ represent organic residues), such as polysiloxane, polytitanoxane, polyaluminoxane, etc., are well known.
These are widely used as lubricants, heat transfer agents, heat-resistant resins, water repellents, adhesives, gelling agents, and the like.
Polymetalloxanes exhibit various properties depending on the type of metal and the type of side chain substituents.
For example, polytitanoxane and polyaluminoxane in which Y ₁ and Y ₂ are alkyl or alkoxy groups have the property that they react with oxygen or water in the air and tend to have hydroxyl groups in their side chains. Polymetalloxane is soluble in small amounts in common organic solvents, such as aliphatic hydrocarbons such as heptane and hexane, and ethers such as diethyl ether, and such organic solvents are generally used. However, when polymetalloxane dissolved in a known organic solvent as mentioned above comes into contact with air or water, the side chain positions are replaced by hydroxyl groups, and as the hydroxyl group content increases, it gels and its solubility in organic solvents is extremely reduced. In addition, polymetalloxane is often used in a highly concentrated state, but in this case, due to its low solubility in solvents, equipment for manufacturing, transporting, and storing polymetalloxane is required. It has disadvantages such as adhering to the equipment used and making it extremely difficult to remove.
The present inventors have proposed a method that does not cause the above-mentioned disadvantages.
That is, as a result of intensive research to find an organic composition that dissolves or solubilizes gel or solid polymetalloxane, it was discovered that a mixture of specific compounds dissolves or solubilizes polymetalloxane extremely well, and the present invention has been made based on this research. It was completed. That is, the present invention [A] General formula

【formula】

【formula】

【formula】

【formula】

【formula】

[Formula] and R ₅ -N=C=O (wherein X ₁ is hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkenyl group, an acyl group, an acyloxy group, a phenyl group, an alkoxy group, an alkoxycarbonyl group, halogen or nitro group, R ₁ and R ₂ are alkyl groups having 1 to 12 carbon atoms,
Alkenyl group or alkoxy group, R ₃ and R ₄ are alkyl groups having 1 to 12 carbon atoms, alkenyl group or hydrogen, R ₅ , R ₆ and R ₇ are carbon atoms 1 to 12
Indicates an integer of an alkyl group having . ) and [B] one compound selected from aliphatic hydrocarbons, aromatic hydrocarbons, and ethers that are liquid under the conditions of use. An object of the present invention is to provide a composition for dissolving polymetalloxane, which is composed of one or more kinds of polymetalloxane.
The present invention will be explained in detail below. The compound [A] used in the composition for dissolving polymetalloxane of the present invention has the general formula

【formula】

【formula】

【formula】

【formula】

【formula】

[Formula] and R ₅ -N=C=O (wherein X ₁ is hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkenyl group, an acyl group, an acyloxy group, a phenyl group, an alkoxy group, an alkoxycarbonyl group , halogen or nitro group, R ₁ and R ₂ are alkyl groups, alkenyl groups or alkoxy groups having 1 to 12 carbon atoms, R ₃ and R ₄ are alkyl groups, alkenyl groups or hydrogen having 1 to 12 carbon atoms , R ₅ , R ₆ and R ₇ have 1 carbon number
an alkyl or alkenyl group having ~12 m
represents an integer from 0 to 5. ) is a compound that can be expressed as Specifically, R ₁ and R ₂ have 1 to 12 carbon atoms, such as a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, etc. Alkyl group; Alkenyl group having 1 to 12 carbon atoms such as vinyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group; methoxy group, ethoxy group, propoxy group , butoxy group, pentoxy group,
Examples include alkoxy groups having 1 to 12 carbon atoms such as hexoxy, heptoxy, and octoxy groups. R ₃ and R ₄ are the same alkyl group, alkenyl group, or hydrogen as shown in R ₁ and R ₂ above,
R ₅ , R ₆ and R ₇ are the same alkyl groups or alkenyl groups as shown for R ₁ and R ₂ above. Specifically, X ₁ is an alkyl group similar to the above-mentioned R ₁ and R ₂ ,
alkenyl groups, alkoxy groups, and acetyl groups,
propionyl group, butyryl group, pentanoyl group,
Acyl groups such as hexanoyl group, heptanoyl group, octanoyl group, acyloxy group such as acetoxy group, propionyloxy group, butyryloxy group, pentanoyloxy group, hexanoyloxy group, heptanoyloxy group, octanoyloxy group, methoxycarbonyl group , ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group,
Examples include alkoxycarbonyl groups such as heptoxycarbonyl group and octoxycarbonyl group, halogens such as fluorine and chlorine, and nitro groups. general formula

Specific examples of the compound represented by the formula include phenol, cresol, ethylphenol, propylphenol,
Butylphenol, pentylphenol, xylenol, diethylphenol, methylethylphenol, dipropylphenol, methylpropylphenol, ethylpropylphenol, trimethylphenol, triethylphenol, monomethyldiethylphenol, monoethyldipropylphenol, methoxyphenol, ethoxyphenol, propoxy Phenol, dimethoxyphenol, diethoxyphenol, trimethoxyphenol, hydroxyacetophenone, propionylphenol, butyrylphenol, diacetylphenol, dipropionylphenol, triacetylphenol, oxystyrene, methyl hydroxybenzoate, ethyl hydroxybenzoate,
Examples include propyl hydroxybenzoate, diethoxycarbonylphenol, dipropoxycarbonylphenol, trimethoxycarbonylphenol, cyanophenol, and the like. general formula

Compounds represented by the formula include acetylacetone, propionylacetone, butyrylacetone, heptane-3.5-
β-diketones such as dione, octane-3.5-dione, β-ketone acid esters such as methyl acetoacetate, methyl propionyl acetate, ethyl acetoacetate, isopropyl acetoacetate, ethyl propionylacetate, propenyl acetoacetate, dimethyl malonate, Examples include malonic acid diesters such as diethyl malonate, methyl ethyl malonate, and methyl vinyl malonate. general formula

Compounds represented by the formula include diacetone alcohol, β-oxyketones such as β-oxyethylmethylketone,
β-oxycarboxylic acid esters such as hydroacrylic acid, general formula

Compounds represented by [Formula] include ethyl glycolate, ethyl lactate, α-
α-oxycarboxylic acid esters such as methyl oxypropionate, α-oxycarboxylic acid esters such as acetol, acetoin, etc.
-Oxyketones, general formula

Compounds represented by the formula include α-amino alcohols such as 2-aminoethanol, 2-amino-2-vinylethanol, 2-aminopropanol, and 2-aminobutanol;

Compounds represented by the formula include N,N dimethylacetamide, N,N diethylacetamide, N,N methylvinylacetamide, N,N dimethylpropionamide, N,
Examples include N-diethylpropionamide. Compounds represented by the general formula R ₅ -N=C=O include alkyl isocyanates such as methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, and pentyl isocyanate, vinyl isocyanate, and propenyl isocyanate. Examples include alkenyl isocyanates such as. Compounds [B] used in the composition for dissolving polyaluminoxane of the present invention include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, nonane, decane, undecane, pentene, hexene, heptene, and octene, benzene,
Aromatic hydrocarbons such as toluene, xylene, trimethylbenzene, styrene, allylbenzene, ethylbenzene, propylbenzene, methyl ether, ethyl ether, methyl ethyl ether, methyl vinyl ether, ethyl vinyl ether, propyl ether, methyl butyl ether, dioxane, pyran, Examples include ethers such as tetrahydrofuran and furan. Compound [A] is a compound that alone does not have the ability to dissolve polymetalloxane. [B] Compound is generally used as a solvent for polymetalloxane, but for example, it has OH in its side chain.
A certain amount or more of the group, for example 5 mol% (based on metal atoms)
It is extremely difficult to dissolve polymetalloxane having the above properties. However, a mixture of compound [A] and compound [B] exhibits significantly superior dissolution ability compared to when each is used alone.
Therefore, a small amount of water or oxygen (several 100 to several 1000 ppm) is present in the atmosphere or solvent,
When a known solvent is used, even when a gelled product is generated, when the dissolving composition of the present invention is used as a solvent, it is possible to maintain a dissolved state without gelation. In the polymetalloxane dissolving composition of the present invention, the mixing ratio of the [A] compound and the [B] compound is as follows:
The weight ratio of [A] compound and [B] compound is 0.1/100
~30/100, preferably 1/100~20/100. [A] If the mixing ratio of the compound is less than 0.1/100 weight ratio, the effect of improving the dissolving ability will be small and undesirable, while if it is more than 30/100 weight ratio, it will become uneconomical. By using this dissolving composition, for example, it is possible to uniformly dissolve polymetalloxane in a high concentration range, making it possible to stabilize operations, and also to dissolve polymetalloxane that has adhered to the inside of towers, tanks, and piping. Removal becomes easier. The polymetalloxane referred to in the present invention has the general formula

[Formula] and/or

[Formula] (wherein M is a trivalent or tetravalent metal atom, Y ₁ and Y ₂ are the same or different hydrogen atoms, organic residues, nitro groups, or halogens) do. In the above general formula, M includes aluminum, gallium, isodium, silicon, germanium, tin, lead, yttrium, titanium, zirconium, rare earth elements (lanthanide series), chromium, manganese, iron, cobalt, nickel, and the like. In particular, aluminum, silicon, titanium,
Suitable for indium and tin polymetalloxanes. In addition, in the above general formula, Y ₁ and Y ₂ are hydrogen atoms, alkyl groups, alkoxy groups, acyl groups, alkoxycarbonyl groups, alkenyl groups, phenyl groups, substituted phenyl groups, nitro groups, halogens such as chlorine, fluorine, etc. Can be mentioned. The composition for dissolving polymetalloxane of the present invention can be suitably used as a raw material for producing polymetalloxane, a solvent for polymetalloxane, etc., or as a cleaning agent for dissolving gelled or solidified polymetalloxane. EXAMPLES The present invention will be explained below using examples, but the present invention is not limited to the following examples. Example 1 A composition of 40 c.c. in which the type and amount of compound [A] shown in Table 1 was dissolved in [B] tetrahydrofuran.
20 g of polyisopropoxyaluminoxane was charged into the solution and stirred at room temperature for 1 hour to examine solubility. The results are shown in Table 1.

[Table] Example 2 As shown in Table 2, 20 g of polyisopropoxy titanoxane was added to 40 c.c. of the composition [B] dissolved in toluene so that the [A] compound was 5% by weight. The solubility was examined by stirring at room temperature for 1 hour.
The results are shown in Table 2.

[Table] Example 3 20 g of polyethoxysiloxane was added to 50 c.c. of a dissolving composition prepared by dissolving [A] compound of the type and concentration shown in Table 3 and [B] diethyl ether, and the mixture was heated at room temperature for 1 hour. The solubility was examined by stirring. The results are shown in Table 3.

【table】

Claims (1)

[Claims] 1 [A] General formula [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] and R ₅ −N=C=O (wherein, X ₁ is hydrogen, the number of carbon atoms Alkyl group, alkenyl group, acyl group, acyloxy group, phenyl group, alkoxy group, alkoxycarbonyl group, halogen or nitro group having 1 to 12 atoms, R ₁
and R ₂ is an alkyl group having 1 to 12 carbon atoms,
Alkenyl group or alkoxy group, R ₃ and R ₄ are alkyl groups having 1 to 12 carbon atoms, alkenyl groups or hydrogen, R ₅ , R ₆ and R ₇ are alkyl groups or alkenyl groups having 1 to 12 carbon atoms , m is 0
Indicates an integer between ~5. ) One or more compounds selected from the compounds represented by [B] One compound selected from aliphatic hydrocarbons, aromatic hydrocarbons, and ethers that are liquid under the conditions of use. Or a composition for dissolving polymetalloxane consisting of two or more types. 2 The mixing ratio of [A] compound and [B] compound is
The composition for dissolving polymetalloxane according to claim 1, characterized in that the weight ratio is 0.1/100 to 30/100. 3 The mixing ratio of [A] compound and [B] compound is
The composition for dissolving polymetalloxane according to claim 1, characterized in that the weight ratio is 1/100 to 20/100. 4 Polymetalloxane is polyaluminoxane,
The composition for dissolving polymetaloxane according to claim 1, 2 or 3, which is polytitanoxane or polysiloxane. 5. The composition for dissolving polymetalloxane according to claim 1, 2 or 3, wherein the polymetalloxane is polyaluminoxane.