KR100454273B1 - A method of hydrotalcite by polyhydric alcohol and polyhydric alcohol ester or metallic substituent and the hydrotalcite made of thereof - Google Patents

Abstract

The present invention relates to a method for producing hydrotalcite having excellent catalytic neutralization ability and a halogen trapping role. The present invention relates to a method for producing a new hydrotalcite which has excellent halogen trapping ability and shows good tendency in heat resistance and lubricity when used in polymers.

Description

A method of hydrotalcite by polyhydric alcohol and polyhydric alcohol ester or metallic substituent and the hydrotalcite made of phosphoric acid and a method for preparing hydrotalcite using polyalcohol and polyhydric alcohol ester or metal substituent

The present invention relates to a method for producing hydrotalcite using polyhydric alcohols and polyhydric alcohol esters or metal substituents, and to hydrotalcites prepared from them. It relates to a method for producing hydrotalcite by complex reaction of substituents and to hydrotalcite prepared from them.

Generally, hydrotalcites are anionic surfactants. Fatty acids, silanes, polyorganosiloxanes, polyorganohydrogensiloxanes or higher fatty acid esters are coated and used in polymers. Therefore, they must satisfy the conditions of high temperature forming temperature and processing conditions and exhibit good tendency to heat resistance and lubricity.

Halogens also have a number of adverse effects on polymers. When the polymer contains halogen, radicals are generated by the halogen, and the generated radicals cause a polymerization reaction during processing, resulting in a high polymerization degree or poor heat resistance. It also corrodes the surface of the machine, shortening its life and damaging the surface of the product. Therefore, there is a need for neutralizing halogens or neutralizing halogen chlorides. Among these neutralizing agents, hydrotalcite is the most effective, and is widely used. These hydrotalcite compounds have a structure of M (II) 1-XM (III) X (OH) ₂ Am-x / m · nH ₂ O, wherein M (II) is Mg ²⁺ , Ni ²⁺ , s, NO ^3-, SO ^2-4, halide ^- Zn ²⁺ or the like M (ⅲ) is ^{Al 3+, Fe 3+, Cr 3+} , and the like Co ^3+, Am- ^2-3 is CO, OH As a mineral composed of halides, it exists as a natural mineral, but natural hydrotalcite not only contains other minerals but also contains a large amount of heavy metals, which is not suitable for use as a polymer additive. Therefore, hydrotalcite is synthesized in high purity and added to the polymer.

Such hydrotalcite may be prepared by using a metal salt such as MgCl ₂ or AlCl ₃ (US Pat. No. 4,351,814, Japanese Patent Application Laid-Open No. 50-30039 and H6-32941) or MgO, Mg Metal oxides such as (OH) ₂ , Al (OH) _3, and methods for producing using hydroxides (US Pat. Nos. 4,904,457 and 5,250,279).

However, the hydrotalcite prepared by the above method has a problem that, when used in a polymer, does not satisfy the conditions at high molding temperature and processing conditions, as well as exhibits poor tendency in heat resistance and lubricity.

The present invention is to solve the problems and problems of the prior art as described above, the surface of the metal by synthesizing the polyhydric alcohol and polyhydric alcohol ester in two stages at the end of the inorganic hydrotalcite-based reaction without the simple surface treatment of the organic metal soap system By using the method of proceeding the drying and crushing process by salting on, it has better halogen trapping ability and physical tendency than the conventional surface treated inorganic system, and also shows excellent tendency in lubrication and heat resistance during processing, In particular, it is an object of the present invention to provide a hydrotalcite having excellent coating property by partial salting on a surface of a polyalcohol-based hydrotalcite and a method of preparing the same.

The present invention for achieving the above object,

In the method for producing a hydrotalcike using a metal oxide or hydroxide,

Putting slurry of water and magnesium hydroxide into a high pressure reactor (S1);

After the step (S1) to put sodium bicarbonate and stirring (S2);

After the step (S2) and the step of adding aluminum hydroxide and reacting to adjust to normal pressure (S3); And,

After adding the polyhydric alcohol after the step (S3) provides a method for producing a hyrotalcite comprising the step (S4).

Here, the water and magnesium hydroxide added to the high pressure reactor in the step (S1) is preferably 1.4 liters of water and 0.7 mol of magnesium hydroxide based on a reactor of 3 liters capacity.

In addition, the sodium bicarbonate in the step (S2) is added 0.48 mol based on the step (S1), the stirring time is 30 minutes.

In addition, the aluminum hydroxide in the step (S3) is added to 0.35 mol based on the step (S1), the reaction conditions are preferably a stirring speed 350rpm, pressure 100psi and the reaction time is 1 hour 30 minutes.

Finally, the polyhydric alcohol in the step (S4) is preferably added to 5% of the solids based on the step (S1) and then stirred for 30 minutes at 175 ℃ again.

After completion of the reaction, filtering and drying are carried out in a conventional manner to obtain a white powder.

And, the polyhydric alcohol used in the present invention,

alkanols, cycloalkanols, n-hexanol, n-heptanol, n-octanol, 2-ethyl hexanol, isooctyl alcohol, octanol-2, 2-methyl heptanol-2, n-decyl alcohol, isodecyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, cyclohexanol, methyl cyclohexanol, alkanediols, ethylene glycol, propylene glycol, trimethylene glycol, 1,2-butylene glycol, 2,3-butylene glycol, 1,4-butylene glycol, 1,6-hexanediol, pinacol, 1,2-pentanediol, 2-methyl-2,4-pentanediol, 1,3-butylene glycol, neopentyl glycol, 2-ethyl-1,3-hexanediol, 2,4-pentanediol, 2,4-heptanediol, 2, One or more selected from the group consisting of 2-diethyl-1,3-propanediol, 2-ethyl-2n-butyl-1,3-propanediol, pentaerythritol, dipentaerythritol can be used.

In addition, the present invention is a hydrotalcite produced by the above-described method, the Na / Al range up to 0.1-3, the polyhydric alcohol and polyhydric alcohol ester or metal substituent is added 0.1-20 Wt% of the final hydrotalcite Provide hydrotalcite.

In addition, when hydrotalcite is prepared using metal oxides or hydroxides, the hydrotalcite may be used for esterification by adding 0.01-5 M mol (Mole) of fatty acids and fatty acid salts, especially stearic acid.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments.

Hydrotalcite is prepared by using metal oxides or hydroxides, and the reaction is performed using Al (OH) ₃ , Mg (OH) ₂ , and NaHCO ₃ . This reaction proceeds by raising the temperature under high pressure in water. At this time, when the reaction is completed, a certain amount of fatty acid RCOOH (R = C8-22) is added to proceed with the additional reaction, and the excess metal hydroxide and residual sodium compound react with the fatty acid to form a metal soap. This is generally very efficient in process compared to finishing the reaction process of hydrotalcite and surface treatment separately. Herein, the present invention adds polyalcohol and polyalcohol ester or polyalcohol metal substituent, proceeds partial esterification and saltation of polyalcohol, and reacts with hydrotalcite according to the intended use to dry and grind. The polyhydric alcohols used here are alkanols, cycloalkanols, n-hexanol, n-heptanol, n-octanol, 2-ethyl hexanol, isooctylalcohol, octanol-2, 2-methyl heptanol-2, n-decyl alcohol , isodecyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, cyclohexanol, methyl cyclohexanol, alkanediols, ethylene glycol, propylene glycol, trimethylene glycol, 1,2-butylene glycol, 2,3-butylene glycol, 1,4- butylene glycol, 1,6-hexanediol, pinacol, 1,2-pentanediol, 2-methyl-2,4-pentanediol, 1,3-butylene glycol, neopentyl glycol, 2-ethyl-1,3-hexanediol, 2,4 -pentanediol, 2,4-heptanediol, 2,2-diethyl-1,3-propanediol, 2-ethyl-2n-butyl-1,3-propanediol, pent One or two or more fatty acids selected from the group consisting of aerythritol, dipentaerythritol and the like and used for esterification are saturated or unsaturated fatty acids having C 1 -C 22 carbon atoms.

RCOOH

aMg (OH) ₂ + bAl (OH) ₃ + cNaHCO ₃ + dH ₂ O ---------->

[Polyhydric alcohol]

MgxAl2 (OH) 2X + 4CO ₃ and nH ₂ O + + yRCOOROH NaM

At this time, the molar ratio (b / a + b) of magnesium hydroxide and aluminum hydroxide is 0.2-0.5, and NaHCO3 is added in the range of 0.1-3. Polyhydric alcohols and polyhydric alcohol esters can be added up to 0.1-20 Wt% of hydrotalcite, and fatty acids to be added if necessary can be adjusted according to Wt% of polyhydric alcohols.

Example 1

1.4 liters of water was added to a 3 liter high-pressure reactor, 0.7 mol of magnesium hydroxide was added to the slurry, and 0.48 mol of sodium bicarbonate was added thereto, followed by stirring for 30 minutes. 0.35 mole of aluminum hydroxide was added thereto, reacted at a stirring speed of 350 rpm and a pressure of 100 psi for 1 hour and 30 minutes, and then adjusted to normal pressure. After the reaction was completed, the filter was dried to obtain a white powder.

Example 2

1.4 liters of water was added to a 3 liter high-pressure reactor, 0.7 mol of magnesium hydroxide was added to the slurry, and 0.48 mol of sodium bicarbonate was added thereto, followed by stirring for 30 minutes. 0.35 mol of aluminum hydroxide was added thereto, and the resultant was reacted at a stirring speed of 350 rpm and a pressure of 100 psi for 1 hour and 30 minutes, and then adjusted to atmospheric pressure. The reaction was stirred for 30 minutes. After the reaction was completed, the filter was dried to obtain a white powder.

Example 3

1.4 liters of water was added to a 3 liter high-pressure reactor, 0.7 mol of magnesium hydroxide was added to the slurry, and 0.48 mol of sodium bicarbonate was added thereto, followed by stirring for 30 minutes. 0.35 mole of aluminum hydroxide was added thereto, reacted at 350 rpm and a pressure of 100 psi for 1 hour and 30 minutes, and then adjusted to atmospheric pressure. 5% of a polyhydric alcohol and 1/2 equivalent of a polyhydric alcohol were added after the polyhydric alcohol was added. The reaction was further stirred at 175 ° C. for 30 minutes. After the reaction was completed, the filter was dried to obtain a white powder.

Thermal stability test

The best way to compare chloride neutralization capacity in polymers is to compare the heat resistance by adding the same amount to the PVC resin. Thus, the specimens of each sample were mixed as shown in Table 1 and kneaded at 30 rpm for 30 minutes at a roll of 130 ° C. to make a heet of about 0.7 mm thickness.

Table 1 Thermal Stability Test Results According to Examples of the Present Invention

division A Example 1 Example 2 Example 3 PVC 50 g 50 g 50 g 50 g DOP 20 g 20 g 20 g 20 g Zn-St 0.5g 0.5g 0.5g 0.5g SAMPLE 1 g 1 g 1 g 1 g

* A: Surface treated hydrotalcite

Each prepared specimen was cut to a certain size, arranged on a glass plate, placed in an oven at 190 ° C., taken out at intervals of 10 minutes, and tested for thermal stability.

Sample elapsed time A Example 1 Example 2 Example 3 10 minutes ◎ ◎ ◎ ◎ 20 minutes ◎ ◎ ◎ ◎ 30 minutes ○ ◎ ○ ◎ 40 minutes △ ○ △ ○ 50 minutes △ △ △ △ 60 minutes △ △ △ △ 70 minutes × △ × △ 80 minutes ×× × × ×

<Table 2> Comparison of heat resistance according to each embodiment of the present invention

◎: Very good, ○: Good, △: Normal, × bad, ××: Very bad

As described above, the present invention provides a simple method of adding polyhydric alcohol and polyhydric alcohol ester or metal substituent during the reaction process in order to produce hydrotalcite having excellent performance in trapping halogen contained in the polymer and improving heat resistance and lubricity. The synthesis method is presented. The composite hydrotalcite thus synthesized can be used as a neutralizer in halogen-containing polymer catalysts, and is very effective for preventing corrosion in products containing halogen flame retardants and protection from weakening of polymers by halogen. , Concrete filler, insulation, heat insulation sheet, antiseptic material, film filler, PVC heat-resistant improver, electrical insulation material and the like can be used in various ways.

Although the preferred embodiments of the present invention have been described in detail with reference to the accompanying drawings, the present invention is not limited thereto and may be improved or modified by those skilled in the art within the scope of the technical idea of the present invention.

Claims (8)

In the method for producing a hydrotalcike using a metal oxide or hydroxide, Putting slurry of water and magnesium hydroxide into a high pressure reactor (S1); After the step (S1) to put sodium bicarbonate and stirring (S2); After the step (S2) and the step of adding aluminum hydroxide and reacting to adjust to normal pressure (S3); And, After the step (S3) after the addition of the polyhydric alcohol and the reaction method (S4) The method of claim 1, wherein the water and magnesium hydroxide added to the high-pressure reactor in the step (S1) is 1.4 liters of water and 0.7 mol of magnesium hydroxide based on the reactor of 3 liters capacity, and in the step (S2) Sodium bicarbonate is 0.48 mol based on the step (S1), the stirring time is 30 minutes, the aluminum hydroxide in the step (S3) is added 0.35 mol based on the step (S1), the reaction conditions are Stirring speed 350rpm, pressure 100psi and the reaction time is 1 hour 30 minutes, the polyhydric alcohol in the step (S4) is added to 5% of the solids based on the step (S1) and then stirred again at 175 ℃ for 30 minutes Hyrotalcite production method characterized in that the reaction. (Correction) The polyhydric alcohol according to claim 2, wherein the polyhydric alcohol is alkanols, cycloalkanols, n-hexanol, n-heptanol, n-octanol, 2-ethyl hexanol, isooctyl alcohol, octanol-2, 2-methyl heptanol-2, n -decyl alcohol, isodecyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, cyclohexanol, methyl cyclohexanol, alkanediols, ethylene glycol, propylene glycol, trimethylene glycol, 1,2-butylene glycol, 2,3-butylene glycol, 1 , 4-butylene glycol, 1,6-hexanediol, pinacol, 1,2-pentanediol, 2-methyl-2,4-pentanediol, 1,3-butylene glycol, neopentyl glycol, 2-ethyl-1,3-hexanediol, 2,4-pentanediol, 2,4-heptanediol, 2,2-diethyl-1,3-propanediol, 2-ethyl-2n-butyl-1,3-propanediol, pentaerythritol or dipentaerythritol The high taltalite production method characterized by using the above. 4. The method of claim 3, wherein the polyhydric alcohol is added with 0.01-5 mol (Mole) of fatty acids and fatty acid salts. The method of claim 4, wherein the fatty acid is a saturated or unsaturated fatty acid having C 1 to C 22 carbon atoms. (Correction) A hydrotalcite prepared by any one of claims 1 to 5 , wherein the range of Na / Al is up to 0.1-3, and the polyhydric alcohol and polyhydric alcohol ester or metal substituent are 0.1- of the final hydrotalcite. Hydrotalcite, characterized in that 20Wt% is added. (Correction) can come in claim 6, wherein the hydrotalcite is a hydrotalcite in height, characterized by Sikkim mixture was added to fatty acids and fatty acid salts 0.01-5 mol (Mole). 8. The hydrotalcite of claim 7, wherein the fatty acid is a saturated or unsaturated fatty acid having C1 to C22 carbon atoms.