KR19980082133A - A method for preparing a new catalyst neutralizer comprising an inorganic catalyst neutralizer and an organic catalyst neutralizer - Google Patents

Abstract

A method for producing a new complex neutralizer having excellent neutralization ability by reacting a hydrotalcite system, which is an inorganic catalyst neutralizer used for neutralizing a residual catalyst of a polymerized polyolefin polymer by a catalytic reaction, and a metal soap system, which is an organic catalyst neutralizer, is disclosed . According to the present invention, a predetermined amount of water is placed in a high-pressure reactor and a predetermined amount of metal hydroxide M (OH) ₂ or metal oxide MO (M = Mg, Zn, Ni, Ca) + Al = 0.2 to 0.5) and sodium bicarbonate (Na / Al = 0.2 to 3) were added and the mixture was heated at a temperature of 160 to 180 ° C for 1 to 2 hours to form a hydrotalcite system. C22) is added to 0.1 to 20 wt% of the hydrotalcite, and the reaction is further carried out at 160 to 180 DEG C for 30 minutes. A metal oxide or a hydroxide or a metal chloride such as Ca (OH) ₂ , Mg (OH) ₂ , Zn (OH) ₂ , CaO, ZnO, MgO, CaCl ₂ , ZnCl ₂ or MgCl ₂ is further added The metal soap and hydrotalcite are reacted together in accordance with the purpose of use to be dried and pulverized.

Description

A method for preparing a new catalyst neutralizer comprising an inorganic catalyst neutralizer and an organic catalyst neutralizer

The present invention relates to a novel catalyst neutralizer having an inorganic catalytic neutralizer and an organic catalyst neutralizer. More particularly, the present invention relates to a process for producing a neutralized catalytic neutralizer by combining a hydrotalcite, an inorganic catalyst neutralizer, and a metal soap, And to a process for producing the same.

Generally, the polymerization of many kinds of polyolefin-based polymers is carried out using a metal chloride as a catalyst. However, in such a case, after the polymerization, the metal chloride used as a catalyst forms radicals inside the polymer, which adversely affects the properties of the polymer and may cause the surface of the mold to be corroded during processing.

In order to solve this problem, the catalyst is removed by a method such as washing, and metal soap is used as a neutralizing agent in order to eliminate the activity of the remaining metal chloride catalyst, and calcium stearate has been mainly used as a metal soap. However, when calcium stearate is used to neutralize a metal chloride catalyst, calcium chloride and stearate are formed again. In this case, calcium chloride has a property of attracting water, and stearate causes a cause of bleed out phenomenon And the heat resistance is lost at high temperature.

To compensate for these shortcomings, petrochemical companies are now using hydrotalcite, an inorganic antacid. The hydrotalcite is very useful because it has a neutralization efficiency because it adsorbs the catalyst chloride in a crystal structure by a certain acid adsorption mechanism and has no property of attracting water like bleach out or bleeding out phenomenon like calcium stearate.

The hydrotalcite-based compound _{M (Ⅱ) 1-X M} (Ⅲ) X (OH) 2 A _x I have a structure of the ^m- _{/ m} and nH ₂ O, where M (Ⅱ) is Mg ^2+, Ni ^{2 +,} Zn ^2+, and the like, such as M (ⅲ) is ^{Al 3+, Fe 3+, Cr 3+} , Co 3+, a m- is ^{_{CO 2- 3, OH -, NO}} 3-, SO 2- 4, It is an inorganic substance composed of halides and exists as natural minerals. However, natural hydrotalcite contains other minerals and contains a large amount of heavy metals, which is not suitable for use as a polymer additive. Therefore, hydrotalcite is synthesized with high purity and added to the polymer.

Examples of the hydrotalcite production method include a method (USP 4,351,814, JP 50-30039, JP 6-32941) in which a metal salt such as MgCl _{2 or} AlCl ₃ is used, and MgO, Mg (OH) ₂ , Al (OH) _3, and the like (USP 4,904,457, USP 5,250,279).

A direct reaction method (USP 4,235,794, JP 54-8606, JP 60-23339) in which a metathesis method (JP 59-74200, JP 54-18810) in which a metal salt is reacted with a metal oxide and a metal oxide and a hydroxide are reacted have.

In the method of reacting with the metal chloride in the hydrotalcite-based neutralizing agent production method, the chloride remaining after the reaction must be washed, and there remains a trace amount of chloride even after washing, which has a disadvantage that it adversely affects the polymer.

SUMMARY OF THE INVENTION The present invention has been made to overcome the above-mentioned problems of the prior art, and it is an object of the present invention to provide a method for neutralizing an inorganic catalyst neutralizing agent and an organic catalyst neutralizing agent, And to provide a novel method for producing a catalyst neutralizing agent which is easy to manufacture.

In order to achieve the above object,

A predetermined amount of water was put into a high-pressure reactor, and a predetermined amount of metallic hydroxide or metal oxide was added to the mixture to form a slurry. Then, a certain amount of sodium bicarbonate was added thereto and stirred for 30 minutes. A certain amount of aluminum hydroxide was added thereto. For 30 minutes to prepare hydrotalcite, adding a predetermined amount of fatty acid by adjusting the pressure to normal pressure, reacting the mixture at 175 DEG C for 30 minutes while stirring, filtering and drying after completion of the reaction, .

Preferably, the metal hydroxide is Ca (OH) ₂ , Mg (OH) ₂ , or Zn (OH) ₂ , and the metal oxide is CaO, ZnO, or MgO.

Preferably, the fatty acid is composed of stearic acid and is added in the range of 0.1 to 20% by weight of the hydrotalcite.

Further, according to the present invention,

A predetermined amount of water was put into a high-pressure reactor, and a predetermined amount of metallic hydroxide or metal oxide was added to the mixture to form a slurry. Then, a certain amount of sodium bicarbonate was added thereto and stirred for 30 minutes. A certain amount of aluminum hydroxide was added thereto. The reaction is carried out for 30 minutes to form hydrotalcite, the fatty acid is added by a predetermined amount by controlling at normal pressure, and then a metal compound selected from the group consisting of metal chlorides, metal hydroxides and metal oxides is added in an amount of 1/2 equivalent of the fatty acid The reaction is carried out at a temperature of 175 ° C for 30 minutes with stirring, and the reaction is completed after the completion of the reaction, followed by drying.

Preferably, the metal chloride is made of CaCl _2, ZnCl _2, or MgCl _2.

Hereinafter, a method of preparing a catalyst neutralizing agent according to preferred embodiments of the present invention will be described in detail.

In the present invention, a method of directly reacting with a metal oxide or hydroxide in the preparation of a composite catalyst neutralizing agent is selected to perform a complex reaction. That is, a method in which various metal soap systems are synthesized in two stages at the end of the inorganic hydrotalcite-based reaction without performing simple surface treatment of the organometallic soap system, and the drying and crushing steps are then conducted.

There is a method of reacting Al (OH) ₃ , Mg (OH) ₂ , and NaHCO ₃ as a method of producing hydrotalcite using a metal oxide or hydroxide. This reaction is carried out by raising the temperature at atmospheric pressure and high pressure in water, and a sodium compound is produced in the water after completion of the reaction. At this time, when a certain amount of fatty acid RCOOH (R = C _8-22 ) is added at the end of the reaction, the excess metal hydroxide and residual sodium compound react with the fatty acid to become metal soap.

This is generally very efficient in the process as compared with the surface treatment of hydrotalcite after completion of the hydrothermal reaction process. If necessary, hydroxides such as Ca (OH) ₂ , Mg (OH) ₂ , Zn (OH) ₂ , CaO, ZnO , And metal oxides such as MgO, or metal chlorides such as CaCl ₂ , ZnCl ₂ , and MgCl _2, so that the metal soap and hydrotalcite are reacted together to suit the intended use, Because it is very effective. The reaction proceeds as shown in the following reaction formula (I).

RCOOH

_{aMg (OH) 2 + bAl (} OH) 3 + cNaHCO 3 + dH 2 O ----------------------- [M (OH) _2, MO, etc. ]

MgXAl ₂ (OH) _{2 X + 4} CO ₃ .nH ₂ O + yRCOONa + z (RCOO) ₂ M]

M = Ca, Zn, Mg, and the like.

At this time, the metal soap reaction is formed as a polar crystalline in an emulsion state, and the metal part has a MICELL structure in which the metal parts face each other to form a highly effective composite structure with hydrotalcite. In this case, the molar ratio (b / a + b) of magnesium hydroxide to aluminum hydroxide is 0.2 to 0.5, and the amount of NaHCO ₃ is in the range of 0.2 to 3 in c / b. The fatty acid RCOOH (R = C _8-22 ) may be added in an amount of 0.1 to 20% by weight of the hydrotalcite, and the metal oxide, hydroxide or metal chloride to be added may be adjusted depending on the weight% of the fatty acid.

Example 1

In a high-pressure reactor having a capacity of 3 liters, 1.4 L of water was added, and 0.7 mol of magnesium hydroxide was added to the slurry. Then 0.48 mol of sodium bicarbonate was added and stirred for 30 minutes. 0.35 mol of aluminum hydroxide was added thereto, and the mixture was reacted at a stirring speed of 350 rpm, a pressure of 100 psi and a temperature of 160 to 180 캜 for 1 to 2 hours, preferably 1 hour and 30 minutes, and then adjusted to normal pressure to obtain stearic acid %, And then reacted at 160 to 180 DEG C, preferably 175 DEG C for 30 minutes with stirring. After completion of the reaction, the reaction mixture was filtered and dried to obtain a white powder.

Example 2

In a high-pressure reactor having a capacity of 3 liters, 1.4 L of water was added, and 0.7 mol of magnesium hydroxide was added to the slurry. Then 0.48 mol of sodium bicarbonate was added and stirred for 30 minutes. 0.35 mol of aluminum hydroxide was added thereto, and the mixture was reacted at a stirring speed of 350 rpm, a pressure of 100 psi and a temperature of 160 to 180 캜 for 1 to 2 hours, preferably 1 hour and 30 minutes, and then adjusted to normal pressure to obtain stearic acid %, Zinc chloride was added in an amount equivalent to 1/2 equivalent of stearic acid, and the mixture was reacted for 30 minutes at a temperature of 160 to 180 DEG C with stirring. After completion of the reaction, the reaction mixture was filtered and dried to obtain a white powder.

Example 3

In a high-pressure reactor having a capacity of 3 liters, 1.4 L of water was added, and 0.7 mol of magnesium hydroxide was added to the slurry. Then 0.48 mol of sodium bicarbonate was added and stirred for 30 minutes. 0.35 mol of aluminum hydroxide was added thereto, and the mixture was reacted at a stirring speed of 350 rpm, a pressure of 100 psi and a temperature of 160 to 180 캜 for 1 to 2 hours, preferably 1 hour and 30 minutes, and then adjusted to normal pressure to obtain stearic acid %, And calcium hydroxide was added in an amount equivalent to 1/2 equivalent of stearic acid, followed by reaction at 160 to 180 DEG C for 30 minutes with stirring. After completion of the reaction, the reaction mixture was filtered and dried to obtain a white powder.

Results and Discussion

Thermal stability test

The best way to compare chloride neutralization capacity in polymers is to compare the heat resistance by adding the same amount in the PVC resin. Therefore, the specimens of the respective samples were compounded as shown in Table 1, and kneaded at 130 rpm for 3 minutes at 30 rpm to obtain a sheet having a thickness of about 0.7 mm.

Table 1. Specimen Preparation

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

* A: commercially available surface treated hydrotalcite

Table 1 to each of the specimens made by blending, as cut to a predetermined size arranged in a glass sheet placed in the oven to 190 ℃ to test the thermal stability was taken out every 10 minutes are shown in Table 2 below.

Table 2. Heat Resistance Big Bridge

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 Xx △ △ △

?: Very good,?: Good,?: Fair, poor: poor,

As described above, according to the present invention, a new catalyst neutralizer having excellent neutralization performance and being easy to manufacture can be obtained by more effectively combining the inorganic catalyst neutralizer of the presently used polymer with the organic catalyst neutralizer. The composite neutralizer thus synthesized can be widely used as a sound absorber, a concrete filler, an insulating material, a thermal insulation sheet, a filler, a filler for a film, a PVC heat resistance improver, and an electrical insulating material in addition to a catalyst neutralizing agent for a polymer. In addition, the catalyst neutralizing agent prepared according to the present invention is superior in neutralization ability and physical tendency to that of the conventional surface-treated inorganic system, and is less inconvenient for mixing with inorganic and organic systems, It is also very advantageous in selecting according to the above.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention as defined by the following claims It can be understood that

Claims (7)

A predetermined amount of water was added to the high-pressure reactor, and a predetermined amount of metal hydroxide or metal oxide was added to the mixture to form a slurry. Then, a certain amount of sodium compound was added thereto and stirred for 30 minutes. A predetermined amount of aluminum hydroxide was added thereto. To 180 ° C. for 1 to 2 hours to form hydrotalcite. After adjusting the temperature to normal pressure, a predetermined amount of fatty acid is added, and then the mixture is reacted at a temperature of 160 to 180 ° C. for 30 minutes with stirring, Filtering and drying the catalyst. The method of claim 1, wherein the metal hydroxide is Ca (OH) ₂ , Mg (OH) ₂ , or Zn (OH) ₂ . The method of claim 1, wherein the metal oxide is CaO, ZnO, or MgO. The method of claim 1, wherein the sodium compound is sodium bicarbonate. The method of claim 1, wherein the fatty acid is made of stearic acid and added in an amount of 0.1 to 20 wt% of the hydrotalcite. A predetermined amount of water was added to the high-pressure reactor, and a predetermined amount of metal hydroxide or metal oxide was added to the mixture to form a slurry. Then, a certain amount of sodium compound was added thereto and stirred for 30 minutes. A predetermined amount of aluminum hydroxide was added thereto. To 180 ° C. for 1 to 2 hours to form a hydrotalcite, adding a predetermined amount of fatty acid by controlling at normal pressure, and then adding a metal compound selected from the group consisting of metal chlorides, metal hydroxides and metal oxides to The reaction is carried out at a temperature of 160 to 180 DEG C for 30 minutes with stirring, and after completion of the reaction, filtration and drying are carried out. 7. The method of claim 6, wherein the metal chloride is CaCl _2, ZnCl _2, MgCl or a method of producing a catalyst neutralizing agent, characterized in that _two.