KR100333404B1 - Novel aluminosiloxane compound and process for preparing the same - Google Patents

Abstract

The present invention relates to novel aluminosiloxane compounds of the general formula (1) or (2), their preparation and the use of these compounds:

Wherein R, n and M are each as defined in the specification.

Description

Novel aluminosiloxane compound and process for preparing the same

The present invention relates to novel aluminosiloxane compounds of the general formula (1) or (2) below, their preparation and the use of these compounds. In particular, the compound of formula 1 or 2 according to the present invention can be prepared by recycling the waste silicon compound, it can be very useful as a siloxane agent for a variety of organic and inorganic materials, in particular, including a hydroxy group Have

[Formula 1]

[Formula 2]

In the above formula

Each R is the same or different and represents C ₁ -C ₆ -alkyl or phenyl,

n represents a number from 6 to 90,

M represents an alkali metal.

Currently used as siloxane agents are hydroxyl group (-OH), alkoxy group (-OR), carboxyl group (-OCOR), amine group (-NHR, -NR ₂ ), epoxy group ( And silane or siloxane compounds containing a hydro group (-H), or a modified silyl compound in which silyl groups exist in a state in which a silyl group is bonded to an intramolecular side chain.

The new aluminosiloxane compound to be provided in the present invention belongs to a heterometal siloxane (Si-OMO-Si≡) series containing metal atoms between siloxane groups. The aluminosiloxane compounds according to the invention can not only replace existing siloxane agents, but also dialkyl (or phenyl) siloxane units ( It is expected to form at least six or more connected long chains to show the properties of the silicon more strongly, and particularly have excellent properties such as siloxane reactivity.

Much research has been done on aluminosiloxanes. For example, the result of synthesizing aluminosilsesquioxane by reacting isopropoxyaluminum [(i-PrO) ₃ Al] with trialkoxysilane is described in J. Am. Chem. Soc. 1989, 111, 7288-7289 and Inorg. Chem. 1999, 38, 210-211), wherein the aluminosylsesquioxane compound synthesized is seen in that aluminum has an AlO ₄ arrangement. The same as the compound according to the invention, but the silicon atom has an arrangement of RSiO ₃ unlike the compound of the present invention. Meanwhile, the aluminum metal surface is treated with ethoxysilane vapor to form an Al—O—SiO bond on the metal surface to prevent corrosion of the metal surface and to give gloss to the surface. the Electrochemical Society V. 143, N. 1, 1996); Treating Al metal surfaces with alkoxysilanes using a sol-gel method to form an Al-O-Si® framework (colloids and Surfaces A: Physicochem. Eng. Aspects 139, 299-310, 1998); A method for synthesizing phosphineruthernium (Rh) complexes by reacting isopropoxyaluminum with an alkoxysilane by a sol-gel method (Inorg. Chem. 1997, 36, 862-866 and Chem. Mater. 1998, 10, 217-225); And methods for ultimately preparing mullite from aluminium and aluminum oxide via aluminosiloxane (Chem. Mater, 1996, 8, 2056-2060), respectively, are known, but any of these disclosed in the prior art Neither intermediates nor targets have similar structures or properties as the novel aluminosiloxane compounds to be provided in the present invention.

Under this technical background, the present inventors solved the pollution problem caused by the discarded silicon compound and furthermore, the effective decomposition and recovery method of siloxane bond-containing compounds such as silicone rubber or silicone oil for the settlement of the silicon chemical industry without worrying about waste. As a result, the development and application of a new decomposition method of the siloxane bond-containing compound, characterized in that the secondary and / or tertiary aliphatic alcohol is used as a decomposition accelerator, and optionally treated with ultrasonic and decomposition stopper It has been patented (see Republic of Korea Patent No. 190,752, US Patent No. 5,892,087). In particular, the siloxane bond has the advantage of excellent weather resistance that does not deteriorate or decay in the air, but this characteristic is rather decomposed and recovered because it is newly emerged as a terrible pollutant because it is connected to a property that cannot be destroyed naturally after use. The development of the method was considered to be of great significance in terms of environmental protection.

The present inventors have not limited to this, and tried to develop a compound that can be usefully used as a siloxane agent as a starting material of the siloxane alkali metal salt of the formula (3) produced through the decomposition method, and as a result While synthesizing the compounds and determining the structure, while identifying their useful uses, the present invention has been completed.

In the above formula

Each R is the same or different and represents C ₁ -C ₆ -alkyl or phenyl,

R 'represents hydrogen or C ₁ -C ₆ -alkyl,

M represents an alkali metal,

m represents the number of 3-6.

Hereinafter, the present invention will be described in more detail.

1 shows G.P.C. (gel permeation chromatography) spectra of the aluminosiloxane compound (Al content 2.76%) of Formula 2 obtained in step 3 of Example 1 (average molecular weight 2000, Mw / Mn = 1.5);

FIG. 2 shows G.P.C. of the aluminosiloxane compound (Al content 2.85%) obtained by heating the aluminosiloxane compound of formula 2 with ammonium chloride in step 3 of Example 1 and then heating. Spectrum is shown (average molecular weight 1000, Mw / Mn = 1.25);

Figure 3 is a G.P.C. of the aluminosiloxane compound (Al content 0.52%) of the formula (1) obtained in Example 5. Spectrum is shown (average molecular weight 5462, Mw / Mn = 1.46);

4 is a G.P.C. of the aluminosiloxane compound (Al content 0.3%) of Formula 1 obtained in Example 6. Spectrum is shown (average molecular weight 10948, Mw / Mn = 1.32);

5 shows the ¹ H-NMR spectrum of the aluminosiloxane compound (average molecular weight 1000) of Formula 1 obtained in Example 1;

FIG. 6 shows a ²⁹ Si-NMR spectrum of an aluminosiloxane compound (average molecular weight 1000) of Chemical Formula 1 obtained in Example 1;

FIG. 7 shows ²⁷ Al-NMR spectra of the aluminosiloxane compound (average molecular weight 1000) of Chemical Formula 1 obtained in Example 1. FIG.

An object of the present invention is to provide an aluminosiloxane compound of formula (1) or formula (2).

[Formula 1]

[Formula 2]

In the above formula

Each R is the same or different and represents C ₁ -C ₆ -alkyl or phenyl,

n represents a number from 6 to 90,

M represents an alkali metal.

As can be seen from the formulas (1) and (2), in the aluminosiloxane compound according to the present invention, the silicon atom is a dialkyl (or phenyl having two oxygen atoms and two alkyl (or phenyl) groups bound around it. Siloxane unit ( ) Was confirmed by ²⁹ Si-NMR, and the aluminum atom was confirmed by the ²⁷ Al-NMR to exist as a tetragon with four oxygen atoms around.

The molecular weight of the compound of the present invention having such an unusual structure varies depending on what is R, M and n. In addition, it is thought that the compound of Formula 1 forms a compound of Formula 2 by two-molecule association according to the content of M. That is, when R is methyl, n is 6, and M is sodium, the compound of formula 2 (sample No. 1 in Table 1) having an average molecular weight of 2000 is treated with ammonium chloride (purification = sodium removal step). GPC decreased significantly (1.51% → 0.55%) As a result of molecular weight measurement, a compound of Formula 1 having an average molecular weight of 1000 (sample No. 2 in Table 1) was obtained. Table 1 below shows the elemental analysis results of several representative compounds according to the present invention and the n value calculated therefrom.

Sample number C (%) H (%) O (%) Si (%) Al (%) Na (%) Molecular Weight Si / Al n value Calculated Value GPC measure One 30.75 6.27 22.88 35.84 2.76 1.51 1963.70 2,000 12 6 2 30.82 6.28 22.89 35.8 2.85 0.55 903.27 1,000 12 6 3 31.59 6.59 23.9 36.82 0.52 0.3 5,250.60 5,462 70 35 4 32.41 7.67 23.21 36.68 0.3 0.2 10,042.70 10,948 130 65

As can be seen from the elemental analysis results of Table 1, in the case of Sample No. 3 (the target of Example 5), the aluminum content was 0.51% and the average molecular weight was 5,462 (see FIG. 3), and Sample No. 4 (the target of Example 6). ), The aluminum content is 0.3% and the average molecular weight is 10,948. Calculated from the elemental analysis results, the n value of Sample 3 is 35 and the n value of Sample 4 is 65. Samples 3 and 4 were prepared using different amounts of aluminum metal powder (see Examples 5 and 6). Therefore, it can be seen that by adjusting the amount of aluminum used as a starting material in the preparation of the aluminosiloxane compound according to the present invention, it is possible to arbitrarily control the value of n, and various molecular weights including the results of elemental analysis of Table 1 above. As a result of performing elemental analysis on the compound of the present invention, it was confirmed that the silicon atoms in the aluminosiloxane compounds of the formulas (1) and (2) according to the present invention were present in a ratio of 12 to 180 atoms per aluminum atom.

In general, the physical properties of the prepared aluminosiloxane compound change according to the change of the n value. For example, as the n value increases, the flexibility increases, but as the n value approaches 90, it is almost in a liquid state, and thus it is not easy to handle (for this reason, in the present invention, the n value is limited to 90 or less). . In addition, depending on the purpose of use, many properties of silicon may be required, while others may require less. Therefore, the aluminium having proper n value can be adjusted according to the use by considering the correlation between n value and physical property. It is preferable to prepare and use a nosiloxane compound.

The aluminosiloxane compound according to the present invention is soluble in nonpolar organic solvents such as n-hexane, benzene, toluene, tetrahydrofuran, stable in specific gravity of 0.94 to 0.98, and stable in the air even as a gel-like solid, It is unstable in the presence of (H ⁺ = proton) and exhibits easily dissociated properties as shown in Scheme 1 below.

Therefore, due to the above properties, organic and inorganic substances containing hydroxyl groups or epoxy groups at the ends thereof, for example, thermosetting resins, cellulose, sucrose, epoxy, etc., and various materials such as epoxy and It is thought that the condensation reaction as shown in Scheme 2 proceeds very actively.

However, when the compound containing a hydroxy group in the reaction scheme 2 is a hydrocarbon compound, if the product is a structure of "Si-O-C", this bond is unstable in the air, so there is a problem that it is easily dissociated again. However, in a thermosetting network resin such as phenol, melamine, urea, epoxy resin, or in a macromolecule such as cellulose, a silicon atom is released into the molecule as the siloxane forms a hybrid structure or dissociates the Si-OC bond. Recombines again into siloxane bonds (≡Si-O-Si≡) to form interpenetrating polymer networks (IPNs) in the polymer, which leads to a stable state, so that these thermosetting resins or macromolecules having macrostructures It is expected that the topic can be used very usefully. In other words, when the aluminosiloxane compound according to the present invention is treated in the final step of preparing macromolecules such as thermosetting resins or cellulose, gloss, flexibility, water repellency, heat resistance, and weather resistance are imparted, thereby improving physical properties of the final processed product. Becomes

In addition, the aluminosiloxane compound according to the present invention can be very usefully used as a siloxane agent for the surface of the superfluid composed of metallic silicate. When the aluminosiloxane decomposes in the presence of acid, or This is because it has a reactive functional group such as (where R is hydrogen or alkyl) and thus easily reacts with the HO-Si 'group on the surface of the superfluid to form a strong bond.

Accordingly, the compound of formula 1 or 2 according to the present invention is a siloxane agent for the surface of thermosetting resins, cellulose, epoxy, metal silicates, pigments composed of various metal oxides and other micro-inorganic substances, compared to silanes containing conventional functional groups. It may be used more usefully, and the present invention has another object to provide such a use. In particular, when the compounds according to the invention are used as siloxane agents, dialkyl (or phenyl) siloxane units ( ) Is siloxaneized in a minimum of 6 to a maximum of 90 units, the siloxane-treated material exhibits a characteristic that the properties of the siloxane are well expressed.

In the siloxaneization using the aluminosiloxane compound which concerns on this invention, a conventional general method can be used. However, when siloxane of the material forming the IPN structure in the siloxane process, such as epoxy resin, the aluminosiloxane compound and the epoxy resin according to the present invention is 9: 1 to 5: 5, preferably 8: 2 to 7 By mixing at a weight ratio of 3: 3 to form a copolymer first, the copolymer may be mixed with an epoxy resin appropriately to effect siloxaneization.

The preferred amount of use when used as the siloxane agent can be easily determined by those skilled in the art according to the structure of the siloxane agent and the specific siloxane agent and the purpose of siloxane, but is usually 2 to 10 based on the siloxane material. The siloxane agent is used in an amount of weight percent, preferably 2 to 6 weight percent. If it is out of this range it is because it is impossible to change the physical properties of the target material in an undesirable direction, or achieve the desired degree of siloxane.

On the other hand, the aluminosiloxane compound of Formula 2 according to the present invention is prepared by reacting the siloxane alkali metal salt of Formula 3 with an aluminum compound and a secondary or tertiary alcohol to prepare a hydrophilic compound of Formula 4 below (2 1) A compound of formula 4 is prepared by reacting with a hydrofluoric acid under a condition of pH 7 to 8 to prepare a compound of formula (5) which is useful, and then (3) to heat the compound of formula (5) at a temperature of 80 to 220 ° C. can do. At this time, in the process of preparing the compound of Formula 2 through the compound of Formula 4 and 5, the number of siloxane units (ie, m 'or m ") is increased by the subsequent condensation reaction, and the degree of increase is aluminum In other words, when the amount of the aluminum compound is input, the condensation reaction is increased, so that the number of siloxane units increases and consequently the n value increases, and when the amount of the aluminum compound is added, the opposite result is obtained. Another object of the present invention is to provide such a manufacturing method.

In the above formula

R and R 'are as defined above,

R "is the same or different and represents R 'or M, but not all represent R',

m 'and m "are each independently the same or different and are numbers such that the n-value range in the resulting compound of Formula 2 is 6-90.

The manufacturing process of the aluminosiloxane compound of Formula 2 may be simplified as shown in Scheme 3 below.

As the siloxane alkali metal salt of Formula 3 in step 1 for preparing the compound of Formula 2, any alkali metal, for example, salts with lithium, sodium, potassium, etc. may be used, but in view of ease of reaction and economical efficiency, sodium salt Preference is given to using. In addition, the aluminum compound used as the reactant may be a salt of an inorganic metal such as aluminum metal, hydroxide of aluminum, oxide, alkali metal salt, halide, sulfuric acid, nitric acid, for example Al, Al (OH) ₃ , Al ₂ O ₃ , AlCl ₃ , AlO ₂ Na may be used, and among these, metal aluminum is preferably used in view of economical efficiency or ease of reaction. The aluminum compound is used in an amount such that the molar ratio of Si / Al in the compound of Formula 2 or 1 is 12 to 180. As mentioned above, the compound of Formula 2 or Formula 1 is finally produced according to the amount of aluminum compound used. N value changes. The reaction proceeds at room temperature or under warming. The reaction temperature may vary depending on the type of aluminum compound used. For example, when metal aluminum is used, the reaction temperature is preferably performed at room temperature, and when aluminum chloride is used, it is necessary to raise the temperature somewhat. The alcohol compound participating in the reaction should be a secondary or tertiary alcohol, with isopropyl alcohol and t-butyl alcohol being particularly preferred. The compound of formula 4 produced through this reaction has the property of being hydrophilic in water.

In step 2, the compound of formula 4 is reacted with hydrofluoric acid under the conditions of pH 7 to 8 to obtain a compound of formula 5. Hydrochloric acid may be used as hydrochloric acid, hydrobromic acid, hydroiodic acid, preferably hydrochloric acid. A basic compound is first added to the reaction solution containing the compound of formula 4 to make the reaction solution alkaline in the pH range of about 8 to about 10, and then hydrochloric acid, which is a reactant, is necessary to adjust the pH of the reaction solution to 7-8. Add in amount and proceed with reaction. At this time, it is preferable to use an ammonia compound, especially ammonia gas or ammonia water, as the basic compound, and the amount of use is sufficient to maintain the liquid phase of the reaction solution in a basic manner. In the case of using an alkali metal-containing compound without using an ammonia compound as the basic compound, for example, further purification may be required depending on the purpose of using the obtained aluminosiloxane compound, which is not preferable. This neutralization process yields a compound of Formula 5 that is oil-miscible and polyfunctional.

Finally, the compound of formula 5 obtained in step 3 is heated to a temperature of 80 to 220 ℃, preferably 100 to 160 ℃ under atmospheric pressure to give the desired compound of formula (2) from which the terminal functional group is removed.

Meanwhile, the aluminosiloxane compound of Chemical Formula 1 according to the present invention, in which M is removed, may be (a) reacting the compound of Chemical Formula 2 with a compound of Chemical Formula 6 in a nonpolar solvent, or (b) a compound of Chemical Formula 7 After reacting with the compound and the secondary or tertiary alcohol, it can be prepared by characterized in that the alcohol is removed.

In the above formula

R, R 'and m are as defined above,

X represents halogen,

R ″ 'represents C ₁ -C ₆ -alkyl.

In the above method (a), it is most preferable to use ammonium chloride in which R 'is hydrogen and X is chlorine among the compounds of formula 6 used as reactants. The reaction is carried out at room temperature and atmospheric pressure for 3 to 5 hours. This is because, when heating the reactants, a problem arises in which the silicone oil is liberated from the resulting aluminosiloxane compound. Since the compound of Formula 6 is used for the purpose of removing M present in the compound of Formula 2, it is preferable to use the compound of Formula 2 in an equimolar amount. In this case, at least one selected from n-hexane, toluene, tetrahydrofuran, benzene and xylene may be used as the nonpolar solvent used as the reaction solvent.

In process (b), the use of the compound of formula (7) as starting material yields the compound of formula (1) directly without the need to use hydrochloric acid. In this case, as the aluminum compound and the secondary or tertiary alcohol compound, the same as those described for the method of preparing the compound of Formula 2 may be used. When the compound of Formula 7 is reacted with an aluminum compound and an alcohol, the reaction may be preferably performed at a temperature of 60 to 80 ° C.

The manufacturing method according to the present invention illustrates a case where an aluminum compound is used, but in addition to the aluminum compound, various forms of zinc (Zn) or tin (Sn) compounds, for example, hydroxides, oxides, alkali metal salts and halogens of these metals Acid addition salts such as cargo, sulfuric acid or nitric acid may also react with the alkali metal siloxane alkali salt of Formula 3 to produce various metalsiloxane compounds in the same manner as the aluminum compound.

Hereinafter, the present invention will be described in more detail based on the following examples. However, these examples are only for the understanding of the present invention, but the scope of the present invention in any sense is not limited to these examples.

Example 1

(Step 1)

100 ml of the siloxane alkali metal salt of formula 3 (R = methyl, R '= isopropyl, M = sodium, m = 3), concentrated to 50% siloxane content, was placed in a 1 L three-necked flask, and sodium aluminate was added thereto. 6 g of sodium aluminate (NaOAlO; Junsei Chemical Co. Lot No. 5K1180), 30 ml of distilled water, and 50 ml of isopropyl alcohol were added thereto, and the reaction mixture was stirred vigorously at room temperature for 3 hours. With continued stirring, it was heated at 40 ° C. for 1 hour and 60 ° C. for 1 hour. The reaction was continued until the reaction became a pale brown transparent liquid. 30 ml of the siloxane alkali metal salt of Chemical Formula 3, which was concentrated to 50% as described above, was further added and stirred continuously until room temperature to obtain a pale brown transparent liquid material (hydrophilic aluminosiloxane metal salt of Chemical Formula 4).

(Step 2)

20 ml of 28% ammonia water was added to the transparent liquid material obtained in step 1, stirred at room temperature for 2 hours, and then the mixture was slowly added dropwise with concentrated hydrochloric acid to adjust the pH of the reaction solution to 7.5. Then it was stirred at 60 ° C. for 1 hour and cooled to room temperature. 100 ml of n-hexane was added, stirred for 30 minutes, and allowed to stand. Then, a supernatant was taken out using a separatory funnel. The supernatant was taken and extracted by adding n-hexane to the remaining lower layer. The extract was combined with the obtained supernatant and washed with distilled water. The oil-soluble aluminosiloxane compound (Formula 5) was obtained by removing the solvent using a rotary evaporator.

(Step 3)

The compound obtained in step 2 was transferred to a 500 ml beaker, concentrated by heating to 150 ° C., and then cooled to cool the aluminosiloxane compound in the form of a gel initial concentrate (Formula 2: R = methyl, M = sodium, n = 6; 60 g of an average molecular weight 2000) was obtained. The obtained initial concentrate was dissolved in 300 ml of n-hexane, and then 3 g of ammonium chloride (molar amount corresponding to the number of moles of alkali metals confirmed by elemental analysis) was added and stirred at room temperature for 4 hours. The supernatant was taken using a separatory funnel, treated with a rotary evaporator, and heated at 150 ° C. to remove the solvent to obtain 59 g of an aluminosiloxane compound (Formula 1: R = methyl, n = 6; average molecular weight 1000). This was dried for 24 hours in a vacuum oven at 30-40 ℃ completely removed the solvent was used as a sample of the structural analysis. By analyzing the samples by ²⁷ Al-NMR and ²⁹ Si-NMR, the structures of AlO ₄ and R ₂ SiO ₂ could be confirmed (see FIGS. 6 and 7).

Example 2

100 ml of the siloxane used as the starting material in Example 1 was placed in a 1 L three-necked flask, where aluminum hydroxide [Al (OH) ₃ ; Aldrich cat. no. 23.918-6] 8 g, 20 ml of distilled water and 50 ml of isopropyl alcohol were added, followed by heating to 40-60 ° C. with stirring. When the reaction product becomes slightly brown translucent, 30 ml of siloxane alkali metal salt of formula (R = methyl, R '= isopropyl, M = sodium, m = 3) is added and the reaction is continued while stirring at the same temperature to give a pale brown transparent liquid. The material was obtained. 20 ml of 28% aqueous ammonia was added to the obtained transparent liquid substance, and concentrated hydrochloric acid was slowly added dropwise while stirring to adjust the pH of the reaction solution to 7.5. The reaction solution was cooled to room temperature, and then 100 ml of n-hexane was added and then allowed to stand. Thereafter, the same procedure as in Example 1 was carried out to obtain 61 g of an aluminosiloxane compound (Formula 2: R = methyl, M = sodium, n = 6; average molecular weight 2000) in the form of a gel initial concentrate, which was converted into ammonium chloride. The treatment gave 58 g of the desired aluminum siloxane compound (Formula 1: R = methyl, n = 6; average molecular weight 1000).

Example 3

Aluminum oxide [Al ₂ O ₃ ; Aldrich cat. no. 23.474-5; 100 mesh] was reacted in the same manner as in Example 1 except for using 5 g of the aluminosiloxane compound in the form of gel-like initial concentrate (Formula 2: R = methyl, M = sodium, n = 6; average molecular weight 2000) 58 g were obtained, thereby obtaining 56 g of an aluminosiloxane compound (Formula 1: R = methyl, n = 6; average molecular weight 1000).

Example 4

The aluminosiloxane compound in the form of a gel-like initial concentrate was reacted in the same manner as in Example 1, except that 2 g of a metal aluminum powder (Aldrich cat. No. 20.258-4) was used as the aluminum compound. 61 g of = methyl, M = sodium, n = 6, average molecular weight 2000) was obtained, and 60 g of an aluminosiloxane compound (Formula 1: R = methyl, n = 6; average molecular weight 1000) was obtained.

Example 5

The reaction was carried out in the same manner as in Example 1, except that 0.4 g of a metal aluminum powder (Aldrich cat.no. 20.258-4) was used as the aluminum compound, and the aluminosiloxane compound of the gel-like semi-solid compound (Formula 1: R = 59 g of methyl, n = 35; average molecular weight 5,462) was obtained.

Example 6

The aluminosiloxane compound of the gel-like semisolid (which is softer than that of Example 5) was reacted in the same manner as in Example 1 except that 0.2 g of metal aluminum powder was used as the aluminum compound (Formula 1: R = methyl , n = 65; average molecular weight 10,948) 60 g was obtained.

Example 7

100 g of methylphenylsilicone oil (from Shintsu, Japan; Kf54) was added to a 500 ml polyethylene container, 100 ml of methanol, 100 ml of isopropyl alcohol, and 12 g of NaOH were added, followed by reaction for 24 hours with shaking at room temperature. While completely decomposing the siloxane alkali metal salt of formula 3 (R = methyl or phenyl, R '= isopropyl, M = sodium, m = 3) was prepared. Thereafter, except that 1.5 g of a metal aluminum powder (Aldrich cat. No. 20.258-4) was used, the reaction was carried out in the same manner as in Example 1, whereby the aluminosiloxane compound of the gel-like semisolid was represented by Chemical Formula 1: R = methyl or Phenyl, n 페닐 7.5; average molecular weight 1,462) 62 g were obtained.

Example 8

100 g of octamethylcyclotetrasiloxane (Aldrich cat.no.23.569-5) was added to a 1 liter polyethylene container, and 100 ml of isopropyl alcohol and tetramethylammonium hydroxide (Aldrich cat. No. 33.490-1, 25% in methanol ) 100 ml were added together and then sealed. The reaction was carried out for 24 hours with shaking at room temperature to completely decompose the silicone oil and at the same time to prepare the siloxane of the formula (R = methyl, R '= isopropyl, R " = methyl, m = 3). Transfer to a three-necked flask and add 1.8 g of metal aluminum powder (Aldrich cat. No. 20.258-4) to a weighted basis, and heat and reflux with stirring at 60-80 ° C. for 20 hours at room temperature for 6 hours. After confirming that the aluminum powder had dissolved and became clear, the mixture was cooled to room temperature, and 300 ml of n-hexane and 100 ml of distilled water were added to the supernatant to separate the supernatant, and the supernatant was evaporated and concentrated in a 500 ml beaker. 94 g (yield 90) of the aluminosiloxane compound (Formula 1: R = methyl, n ≒ 6; average molecular weight 1,120) of a gel semi-solid was removed by leaving the solvent for 48 hours in a vacuum oven (40torr, 50 ℃). %) It was obtained.

Example 9

100 mL of the siloxane alkali metal salt of formula 3 (R = methyl, R '= isopropyl, M = sodium, m = 3) used as starting material in Example 1 was placed in a 1 L three-neck flask, and isopropyl alcohol was added thereto. 100 ml and 100 ml of n-hexane were added. After attaching the reflux condenser to the flask, while stirring vigorously, aluminum chloride [AlCl ₃ · 6H ₂ O; Aldrich cat. no. 23.707-8] was added and heated to 60 ° C. for reaction. When bubbles are generated and the reaction is too vigorous, the temperature is slightly lowered and controlled. When the pH of the reaction solution is not 7.5, aluminum chloride is further added to adjust the temperature to 7.5. After stirring for 1 hour at this temperature, heating and standing, a clear supernatant was taken and washed three times with distilled water. Thereafter, the same procedure as in Example 1 was carried out to obtain 55 g of the aluminosiloxane compound (Formula 2: R = methyl, M = sodium, n = 6; average molecular weight 2000) in the form of a gel initial concentrate, from which the aluminum siloxane compound was obtained. 53 g of (Formula 1: R = methyl, n = 6; average molecular weight 1000) was obtained.

Example 10: Siloxylation of Cellulose

100 g of the compound of Formula 1 having an average molecular weight of 1000 prepared in Example 1 was dissolved in 500 ml of n-hexane, of which 100 ml was taken and 10 g of cellulose fiber fabric was deposited thereon. Dried in air, soaked in 0.5 ml of formic acid and dried again. The dried fabric was heat treated to 130-150 ° C. to siloxane the hydroxyl groups on the cellulose surface. Annals of the acylated cellulose has been given a water repellency was confirmed under a microscope (contact analyzer) that the contact angle of water drop ^O 100-110.

Example 11: Siloxylation of Novolak Phenolic Resin

10 g of novolak phenol resin (molecular weight 600-1500) was dissolved in 50 ml of n-butanol, and finely ground sawdust was added to the phenol resin in a 1: 1 weight ratio and mixed well. The solvent was removed by treatment with a warm air at 50 ° C. and pulverized well by a pulverizer. Then, a solution obtained by dissolving 2 g of a compound of formula 1 having an average molecular weight of 1000 prepared in Example 1 was mixed in 10 ml of n-hexane. The mixture was mixed well and then aged for 24 hours at room temperature. The mixture was put into a mold having a shape, and heated to about 150 ° C. to be compressed and degassed. The siloxane-treated phenolic resin thus prepared did not liberate silicone oil on the surface, did not require the use of a release agent during processing, showed gloss, and improved physical properties with increased flexibility.

Example 12: Siloxylation Reaction of Epoxy Resin

10 g of the compound of Formula 1 having an average molecular weight of 1000 prepared in Example 1 was dissolved in 30 ml of xylene. 2 g of an epoxy resin (Kukdo Chemical YD-011) having a molecular weight of about 800 to 1000 prepared from bisphenol-A and epichlorohydrin was added to the aluminosiloxane xylene solution, dissolved with stirring, and heated at 140-150 ° C. for 20 minutes. . The reaction mixture was cooled to room temperature while continuing to stir, 10 ml of xylene was added, and 15 g of epoxy resin (YD-011) was added thereto. After dissolving and mixing with vigorous stirring at 60-80 ° C, the mixture was cooled to room temperature and G-1034 (Kukdo Chemical) as a curing agent was added at a 1/4 weight ratio to the epoxy resin. The product was applied to the plate glass surface at a thickness of 0.3-0.4 mm and cured at room temperature for 4 days. The surface was then observed, 1) the adhesion to the glass surface was significantly higher, 2) the glass of silicone oil component was not observed on the surface, and 3) the elasticity on the surface was greater than that coated with unsiloxaneed epoxy resin. And 4) excellent surface glossiness.

According to the present invention, not only can the waste silicon material be recycled, but also high utilization of the recycled product can be achieved. That is, when a substance containing siloxane bonds is discarded, the aluminosiloxane compound of formula (1) or (2) can be used to make it possible to use it as a useful siloxane agent.

Claims (13)

An aluminosiloxane compound of Formula 1 [Formula 1] In the above formula Each R is the same or different and represents C ₁ -C ₆ -alkyl or phenyl, n represents the number of 6-90. An aluminosiloxane compound of formula (II) [Formula 2] In the above formula Each R is the same or different and represents C ₁ -C ₆ -alkyl or phenyl, n represents a number from 6 to 90, M represents an alkali metal. (1) reacting a siloxane alkali metal salt of formula (3) with an aluminum compound and a secondary or tertiary alcohol to prepare a compound of formula (4), and (2) a compound of formula (4) with hydrohalide acid under conditions of pH 7-8 Reacting to prepare a compound of formula (5) and then (3) heating the compound of formula (5) at a temperature of 80 to 220 ° C. to produce the aluminosiloxane compound of formula (2) as defined in claim 2. [Formula 3] [Formula 4] [Formula 5] In the above formula Each R is the same or different and represents C ₁ -C ₆ -alkyl or phenyl, Each R 'is the same or different and represents hydrogen or C ₁ -C ₆ -alkyl, M represents an alkali metal, m represents a number from 3 to 6, R "is the same or different and represents R 'or M, but not all represent R', m 'and m "are each independently the same or different and are numbers such that the n-value range in the resulting compound of Formula 2 is 6-90. 4. A process according to claim 3, wherein the value of n in the compound of formula (2) is finally obtained by controlling the amount of aluminum compound used in step (1). The process according to claim 3 or 4, wherein the aluminum compound is used in step (1) in an amount such that the molar ratio of Si / Al is from 12 to 180. The method according to claim 3 or 4, wherein the aluminum compound in step (1) is one selected from aluminum metal, hydroxide of aluminum, oxide, alkali metal salt, halide and inorganic acid salt. 4. The process according to claim 3, wherein in step (2), a basic compound is added to the reaction solution containing the compound of formula (4) to make it alkaline, and then hydrochloric acid is added in an amount necessary to adjust the pH of the reaction solution to 7-8. The method according to claim 7, wherein the basic compound is ammonia gas or ammonia water. 8. The method of claim 7, wherein the hydrofluoric acid is at least one selected from hydrochloric acid, hydrobromic acid, and hydroiodic acid. (a) reacting a compound of formula 2 as defined in claim 2 with a compound of formula 6 in a nonpolar solvent, or (b) reacting a compound of formula 7 with an aluminum compound and a secondary or tertiary alcohol A process for preparing the compound of formula 1 as defined in claim 1, characterized in that the alcohol is removed. [Formula 6] [Formula 7] In the above formula R, R 'and m are as defined in claim 3, X represents halogen, R ″ 'represents C ₁ -C ₆ -alkyl. The method of claim 10, wherein the compound of formula 6 is used in equimolar ratio relative to the compound of formula 2. The process according to claim 10, wherein the reaction in process (b) is carried out at a temperature between 60 and 80 ° C. A siloxane agent, characterized in that it contains a compound as defined in claim 1.