KR101905163B1 - Supporting particle - Google Patents

Abstract

The present invention relates to carrier particles. The carrier particles can sufficiently satisfy the particle characteristics required for use as a spherical carrier for an olefin polymerization catalyst while containing an antioxidant. These carrier particles contain an antioxidant but do not affect the activity of the olefin polymerization catalyst. Therefore, when such carrier particles are used, the olefin polymer which can be extruded and molded without using any antioxidant in the olefin polymerization process and / or the olefin polymer extrusion process, or without deterioration of physical properties due to oxidation, Can be efficiently provided.

Description

Support particles {SUPPORTING PARTICLE}

The present invention relates to carrier particles.

Ziegler-Natta catalysts have been used to polymerize olefins such as ethylene and propylene. The shape and size of the polymers polymerized using Ziegler-Natta catalysts are directly influenced by the shape and size of the catalyst used. Therefore, in order to increase the productivity, to make the particle size of the polymer uniform, and to produce a polymer favorable for product molding, the technique of controlling the size distribution of the catalyst is very important, which is directly related to the size distribution of the carrier. Accordingly, it is very important to produce a carrier particle having a narrow particle size distribution and a solid spherical shape.

As a method of producing such a carrier, recrystallization, spray drying and precipitation are widely used. However, in the case of the spray drying method, the production time is very long and the production cost is high. In the case of the precipitation method, a large amount of hydrogen is generated during the manufacturing process. Further, in the case of the recrystallization method, a particle size distribution is widely formed, and a secondary process such as classification is essentially required to obtain particles having a desired size after the production.

On the other hand, polymers polymerized using such catalysts may be discolored due to oxidation during the extrusion process, or their physical properties may be changed. Thus, antioxidants are added in the course of preparing polymers or extruding polymers to suppress discoloration of polymers and to protect their physical properties. However, when an antioxidant is added to the polymer in the course of preparing the polymer, the activity of the olefin polymerization catalyst is weakened and the production amount of the polymer is decreased. Further, in the process of extruding the polymer, the antioxidant is not well dispersed in the polymer, so that an excessive amount of antioxidant must be added to prevent oxidation of the polymer.

The present invention is to provide a carrier particle having a narrow particle size distribution and a spherical shape, which contains an antioxidant.

According to an embodiment of the present invention, a homogeneous solution prepared by mixing oil, magnesium halide, alcohol having 1 to 5 carbon atoms and an antioxidant is prepared by cooling in the presence of a hydrocarbon solvent having 6 or more carbon atoms, mmol < / RTI >

The carrier particle may include a compound having a structure represented by the following formula (1) as the antioxidant.

[Chemical Formula 1]

In Formula 1,

n is an integer of 1 to 4,

R is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 35 carbon atoms, An alkylaryl group having 7 to 35 carbon atoms, an arylalkenyl group having 8 to 40 carbon atoms, a heteroaryl group having 5 to 30 carbon atoms, an arylamine group having 6 to 30 carbon atoms, a heteroarylamine group having 5 to 30 carbon atoms, Is an alkyl group having 1 to 5 carbon atoms bonded through the intermediacy of -O-, -S-, -CONH-, -COO- or -OCO-,

When n is an integer of 2 to 4, a plurality of Rs may be the same or different, and a carbon which is not substituted with R is bonded to hydrogen.

Specifically, the carrier particles may be the same or different and each independently represents a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec- tert-butyl group, and the like.

More specifically, the carrier particles are selected from the group consisting of 2,6-di-tert-butyl-4-methylphenol (BHT), pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], methyl 3- (3,3- Di-tert-butyl-4-hydroxyphenyl) propionate, 2,2-methylenebis (4-methyl- 6-tert-butylphenol), 2,2-methylenebis (4-methyl-6-tert-butylphenol), stearyl- Stearyl-β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5- 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 3,5- Dimethylethyl) -4-hydroxybenzenepropionic acid thio-2,1-ethanediyl ester (3,5-bis (1,1-dimethylethyl) -4-hydroxybenzenepropanoic ac (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide] (N, N'- Propane-1,3-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide], 4-hydroxy-3,5-di- (3,5-di-tert-butylphenylpropionic acid), 1,1-bis (3,5-di- -tert-butyl-2-hydroxyphenyl) ethane, 4,4'-methylenebis (2,6-di-tert-butylphenol) , Triethylene glycol bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, Bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl) hydrazine, 1,2-bis Bis (6-tert-butyl-p-cresol), diethyl 3,5-di-tert-butyl-4-hydroxybenzyl Pe Diethyl tert-butyl-4-hydroxybenzyl phosphate and 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert- ) Benzene (1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene) .

The carrier particles may have an average particle diameter (D ₅₀ ) of 35 to 90 탆 and a particle size distribution index of 1.00 to 1.80.

The carrier particles may be represented by the following formula (2).

(2)

MgX _m (ROH) _z (AO) _{(6- (m + z))}

M is an integer of 0 to 2, z is an integer of 1 to 6, and the sum of m + z is 3 (wherein R < 3 > is an alkyl group having 1 to 5 carbon atoms; AO is an antioxidant; Lt; / RTI >

The carrier particles may be carrier particles for a propylene polymerization catalyst.

The carrier particles according to one embodiment of the present invention can sufficiently satisfy the particle characteristics required for use as a spherical carrier for an olefin polymerization catalyst while containing an antioxidant. These carrier particles contain an antioxidant but do not affect the activity of the olefin polymerization catalyst. Therefore, when such carrier particles are used, the olefin polymer which can be extruded and molded without using any antioxidant in the olefin polymerization process and / or the olefin polymer extrusion process, or without deterioration of physical properties due to oxidation, Can be efficiently provided.

Hereinafter, carrier particles and the like according to specific embodiments of the invention will be described.

According to an embodiment of the present invention, a homogeneous solution prepared by mixing oil, magnesium halide, alcohol having 1 to 5 carbon atoms and an antioxidant is prepared by cooling in the presence of a hydrocarbon solvent having 6 or more carbon atoms, mmol < / RTI >

The carrier particles of one embodiment of the invention may contain an antioxidant, but may have a narrow particle size distribution and a solid and spherical shape. In addition, the carrier particles contain an antioxidant but do not affect the activity of the olefin polymerization catalyst. Therefore, the carrier particles are used as a carrier for olefin polymerization catalysts due to these properties, so that they have uniform size and good flow properties and do not use antioxidants in the olefin polymerization process and / or the olefin polymer extrusion process, It is possible to provide a polyolefin which can be extruded and molded without any discoloration due to oxidation or a change in physical properties. Particularly, the carrier particles are used as a carrier for a propylene polymerization catalyst, and this effect can be maximized.

Wherein the carrier particles are prepared by mixing oil, magnesium halide, an alcohol having 1 to 5 carbon atoms and an antioxidant to prepare a homogeneous solution; And a second step of cooling the homogeneous solution obtained in the first step in the presence of a hydrocarbon solvent having 6 or more carbon atoms to prepare carrier particles.

In the first step, a homogeneous solution is prepared by mixing oil, magnesium halide, alcohol having 1 to 5 carbon atoms and an antioxidant. At this time, an alcohol having 1 to 5 carbon atoms may be mixed with 1.5 to 5 mol or 2.0 to 3.5 mol based on 1 mol of the magnesium halide to provide a carrier particle having a spherical uniform particle size distribution even though it contains an antioxidant.

If the content of the alcohol having 1 to 5 carbon atoms is less than the above range, the carrier particles are obtained in the form of a lump, and the average particle size becomes excessively large. If the content is in excess of the above range, the fine particles and the spherical particles coexist, have. In addition, there is a fear that the particle size distribution of the carrier particles may be widely formed. However, when the magnesium halide and the alcohol are used in the above-mentioned range, the magnesium halide shows good solubility in the alcohol, the content of the residual alcohol is small after the production process of the carrier particles and the oil or the hydrocarbon solvent can be easily reused, When the catalyst is produced by using the particles, the alcohol rapidly escapes from the carrier particles and cracks on the surface of the carrier particles or the carrier particles are less likely to be broken.

As the magnesium halide, at least one selected from the group consisting of magnesium chloride, magnesium bromide, and magnesium iodide may be used, and magnesium dichloride may be preferably used.

Examples of the alcohol having 1 to 5 carbon atoms include alcohols selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, isopentanol, neopentanol and cyclopentanol Or more, and preferably ethanol may be used.

If the viscosity is less than the above range, it is difficult to form carrier particles having a uniform particle size distribution, and if the viscosity exceeds the above range There is a problem that the yield is significantly lowered due to the carrier particles adhered to the wall of the cooling reactor. As the oil satisfying the viscosity range as described above, paraffin oil, silicone oil or kerosene can be used. The oil may be used at about 500 mL to 2,500 mL per mol of the magnesium halide.

As the antioxidant, additives which are used for preventing deterioration such as decomposition or discoloration of the olefin polymer may be used. Antioxidants are used for the purpose of preventing quality deterioration in the production of plastics, improving the production efficiency, and maintaining the quality of molded products to increase added value. Particularly, the phenolic antioxidant is known as a primary antioxidant as a radical scavenger and serves to protect the resin during plastic processing or during the period of using the finished product. Requirements for antioxidants for plastics should generally be non-toxic, safe at the processing temperature, free from activity and other resin processability, and good miscibility with the resin. It should not cause any chemical reaction with other additives and should be compatible with resin powders, pellets and the like. In general, polypropylene uses more antioxidants in the extrusion process because it is more easily oxidized than polyethylene. As the antioxidant used for extruding polypropylene, it is preferable to use a phenol-based antioxidant of a polymer type which exhibits low volatility when processing or using polypropylene under harsh conditions.

As the antioxidant, a compound having a structure represented by the following general formula (1) may be used.

[Chemical Formula 1]

In Formula 1,

n is an integer of 1 to 4,

R is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 35 carbon atoms, An alkylaryl group having 7 to 35 carbon atoms, an arylalkenyl group having 8 to 40 carbon atoms, a heteroaryl group having 5 to 30 carbon atoms, an arylamine group having 6 to 30 carbon atoms, a heteroarylamine group having 5 to 30 carbon atoms, Is an alkyl group having 1 to 5 carbon atoms bonded through the intermediacy of -O-, -S-, -CONH-, -COO- or -OCO-,

When n is an integer of 2 to 4, a plurality of Rs may be the same or different, and a carbon which is not substituted with R is bonded to hydrogen.

Specifically, as the antioxidant, n is 2 in the formula (1), two R's are the same or different and each independently represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, Butyl group or tert-butyl group can be used.

Examples of compounds containing such a structure include 2,6-di-tert-butyl-4-methylphenol (BHT), pentaerythritol tetrakis [3- (3, (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], methyl 3- (3,3- Di-tert-butyl-4-hydroxyphenyl) propionate, 2,2-methylenebis (4-methyl- 6-tert-butylphenol), 2,2-methylenebis (4-methyl-6-tert-butylphenol), stearyl- Stearyl-β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5- 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 3,5- Dimethylethyl) -4-hydroxybenzenepropionic acid thio-2,1-ethanediyl ester (3,5-bis (1,1-dimethylethyl) -4-hydroxybenzenepropanoic a cid thiodi-2,1-ethanediyl ester), N, N'-propane-1,3-diylbis [3- (3,5- Propane-1,3-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide], 4-hydroxy-3,5-di- (3,5-di-tert-butylphenylpropionic acid), 1,1-bis (3,5-di- -tert-butyl-2-hydroxyphenyl) ethane, 4,4'-methylenebis (2,6-di-tert-butylphenol) , Triethylene glycol bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, Bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl) hydrazine, 1,2-bis Bis (6-tert-butyl-p-cresol), diethyl 3,5-di-tert-butyl-4-hydroxybenzyl Diethyl tert-butyl-4-hydroxybenzyl phosphate and 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert- ) Benzene (1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene).

In the first step, the antioxidant may be mixed with 1 mmol to 50 mmol based on 1 mol of the magnesium halide. Accordingly, the carrier particles prepared through the first and second steps may contain 1 to 50 mmol of antioxidant per 1 mol of magnesium atom. Within this range, the carrier particles can sufficiently satisfy the particle characteristics required for use as a spherical carrier without affecting the activity of the olefin polymerization catalyst.

In the first step, the oil, the magnesium halide, the alcohol having 1 to 5 carbon atoms, and the antioxidant can be mixed in the temperature range of 110 to 130 ° C.

In this temperature range, the magnesium halide is sufficiently dissolved, and even if the homogeneous solution is transferred in the subsequent step, the carrier temperature can be prevented from rising sharply, and carrier particles having a spherical shape and uniform particle size distribution can be formed. In addition, since the binding force between magnesium halide and alcohol is weak, problems that may occur in forming a carrier can be effectively prevented, and the vapor pressure of the obtained homogeneous solution can be adjusted to an appropriate level.

In the first step, the oil, the magnesium halide, the alcohol having 1 to 5 carbon atoms and the antioxidant may be mixed or mixed while stirring at a speed of 400 to 10,000 rpm.

Within this range of stirring speeds, emulsions in which the magnesium halide is completely dissolved are well formed, and spherical carrier particles free from physical damage can be produced in an appropriate size. The stirring time is not particularly limited, but can be adjusted to about 20 minutes to 2 hours.

If a homogeneous solution is obtained through the first step, the homogeneous solution may be cooled in the presence of a hydrocarbon solvent having 6 or more carbon atoms according to the second step to provide carrier particles.

The cooling method in the second step is not particularly limited, but quenching at a rapid rate is advantageous for producing spherical carrier particles. Therefore, although a low-temperature hydrocarbon solvent may be added to a reactor containing a homogeneous solution (hereinafter referred to as a first reactor), it is advantageous to add a homogeneous solution to a reactor containing a low-temperature hydrocarbon solvent (hereinafter referred to as a second reactor).

Specifically, the homogeneous solution obtained in the first step is stirred at 600 to 10,000 rpm and then added to a hydrocarbon solvent having 6 or more carbon atoms. At this time, if the stirring speed is out of the above range, more fine particles are formed and carrier particles having uneven particle size distribution and shape are formed. The stirring time is not particularly limited and may be adjusted to 10 minutes to 2 hours.

On the other hand, in order to quench the homogeneous solution, a hydrocarbon solvent having 6 or more carbon atoms may be added to the second reactor and the temperature thereof may be adjusted to -20 to 20 캜. By controlling the temperature of the hydrocarbon solvent in this way, it is possible to manufacture carrier particles having a hard and uniform shape, and the energy cost can be minimized and the production cost can be saved.

Examples of the hydrocarbon solvent having 6 or more carbon atoms usable herein include at least one selected from the group consisting of hexane, heptane, decane, mineral oil, silicone oil and kerosene. The hydrocarbon solvents having 6 or more carbon atoms may be used alone Or a mixture of two or more of them may be used. Particularly, as the hydrocarbon solvent having 6 or more carbon atoms, hexane is preferably used. The upper limit of the carbon number of the hydrocarbon solvent is not particularly limited and may be about 100 or less.

The amount of the hydrocarbon solvent having a carbon number of 6 or more can be adjusted so that the volume ratio of the oil and the hydrocarbon solvent used in the first step is 1: 2 to 1: 6. It is possible to prevent accumulation of carrier particles within such a range, to appropriately maintain the temperature of the reactor, effectively prevent generation of fine particles, and prevent the problem of increase in production cost.

The homogeneous solution stirred at a specific rate as described above may be added to the second reactor containing the hydrocarbon solvent at a suitable rate. Specifically, the transfer rate of the homogeneous solution may be increased stepwise within a flow rate range of 1 to 8 mL / sec. If the initial feed rate is controlled to be slower than 1 mL / sec, particles may form agglomerates like gel, and if the later feed rate is adjusted faster than 8 mL / sec, the emulsion will cool too rapidly, Clusters can be formed. Also, solid lumps can be generated even if the feed speed is adjusted to be the same from beginning to end.

When the homogeneous solution is supplied to the second reactor, the homogeneous solution may be injected in a hydrocarbon solvent or a hydrocarbon solvent. However, in order to effectively suppress the aggregation of particles, the homogeneous solution may be supplied to the second reactor in a state of air spraying.

When the homogeneous solution is supplied, the hydrocarbon solvent is agitated and the aggregation phenomenon of the particles can be effectively suppressed. The stirring speed of the hydrocarbon solvent can be controlled at 300 to 1000 rpm, and the aggregation of particles can be effectively suppressed without physical damage of the carrier particles within this range.

The carrier particles prepared by cooling the homogeneous solution in a hydrocarbon solvent according to the second step can be purified and / or dried as known to the technical field of the present invention. As an example, the carrier particles obtained in the second step are obtained in the form of a slurry. In order to remove unreacted alcohol or the like from the product in the form of slurry, the carrier particles used in the second step may be added to the product in the form of a slurry and stirred to remove the upper layer solution, so that the carrier particles can be washed 2 to 3 times . At this time, the stirring speed and time may be adjusted to 200 to 800 rpm and 5 to 30 minutes. Within this range, the carrier particles in the form of loose particles are loosened to obtain carrier particles having a uniform particle size distribution without physical damage, The reactants can be effectively removed. If the cleaning process is repeated many times, fine particles may be generated, which is not preferable. The carrier particles thus cleaned can be ventilated under flowing nitrogen for 30 minutes or longer, and the solvent can be completely removed by using a vacuum pump to dry.

The carrier particles produced through the first and second steps may be represented by the following formula (2).

(2)

MgX _m (ROH) _z (AO) _{(6- (m + z))}

M is an integer of 0 to 2, z is an integer of 1 to 6, and the sum of m + z is 3 (wherein R < 3 > is an alkyl group having 1 to 5 carbon atoms; AO is an antioxidant; Lt; / RTI >

Specifically, X may be at least one selected from the group consisting of Cl, Br and I, depending on the type of magnesium halide, and R may be a methyl group, ethyl group, n-propyl group, isopropyl An n-butyl group, an isobutyl group, an n-pentyl group, an isopentyl group, a neopentyl group, and a cyclopentyl group.

These carrier particles are spherical and homogeneous in particle size distribution, and the content of fine particles having a particle size of 10 탆 or less is extremely small at 10% by weight or less, so that a carrier suitable for preparing a catalyst capable of sufficiently satisfying the properties required in the propylene polymerization process .

Also, the carrier particles are suitable for use as a carrier for a catalyst which is required in a conventional commercial polymerization process such as slurry, bulk or gas-phase polymerization, with an average particle diameter (D ₅₀ ) of 35 to 90 탆 and a particle size distribution index of 1.00 to 1.80.

BRIEF DESCRIPTION OF THE DRAWINGS The above and other objects, features and advantages of the present invention will be more apparent from the following detailed description taken in conjunction with the accompanying drawings, in which: FIG. However, this is provided as an example of the invention, and the scope of the invention is not limited thereto in any sense.

Example  One: carrier  Manufacturing of particles

The 1 L of the first reactor equipped with the stirrer and the oil circulation heater was ventilated with nitrogen and dried at 120 DEG C for 2 hours.

In the first reactor, 16.0 g of anhydrous magnesium dichloride, 29.4 mL of ethanol and 2, 6-di-tert-butyl-4-methylphenol ; BHT) and 250 mL of oil (29.7 cSt, 40 DEG C) were charged and stirred at 120 DEG C at a rotation speed of 400 rpm for 1 hour.

On the other hand, a 2 L second reactor equipped with a stirrer and an oil circulation heater was ventilated with nitrogen and dried at 120 DEG C for 2 hours. Thereafter, 1 L of hexane was added to the second reactor, the temperature was lowered to -20 DEG C, and the rotation speed of the stirrer was maintained at 500 rpm.

The homogeneous solution completely dissolved in the magnesium compound present in the first reactor was stirred at a rotation speed of 1000 rpm for 30 minutes and immediately transferred to the second reactor prepared through the transfer line. The feed rate in the transfer line was adjusted stepwise within a flow rate range of 1 to 6 mL / sec using the pressure difference between the dissolution reactor (first reactor) and the quench reactor (second reactor). At this time, the transfer line was set to be spaced apart at regular intervals in the cooling solvent contained in the second reactor.

The homogeneous solution transferred through the transfer line was injected into the second reactor by air spraying method. 190 mL of homogeneous solution was added to the second reactor, then maintained at -16 DEG C for 15 minutes, and the second reactor temperature was raised to room temperature. 1 L of hexane was added to the product obtained in the form of slurry, and the mixture was stirred at 250 rpm for 10 minutes. Subsequently, when stirring was stopped, when the carrier particles had settled, the upper layer solution was removed to remove hexane, unreacted alcohol and oil. After such a washing operation was repeated twice, the carrier was transferred to a 500 mL flask, ventilated under flowing nitrogen for 10 minutes, and dried using a vacuum pump for 30 minutes. 15.8 g of spherical carrier particles were obtained in this manner.

Example  2: carrier  Manufacturing of particles

Carrier particles were prepared in the same manner as in Example 1, except that the content of the antioxidant BHT in Example 1 was adjusted to 0.37 g.

Example  3: carrier  Manufacturing of particles

Carrier particles were prepared in the same manner as in Example 1, except that the content of the antioxidant BHT was adjusted to 0.56 g in Example 1.

Example  4: carrier  Manufacturing of particles

Example 3 was repeated except that pentaerythritol tetrakis [3- (3,5-di (tert-butyl) -4-hydroxyphenyl] -tert-butyl-4-hydroxyphenyl) propionate]) (0.99 g).

Example  5: carrier  Manufacturing of particles

Except that 1.98 g of pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] was used in place of BHT as an antioxidant in Example 1 To prepare carrier particles.

Example  6: carrier  Manufacturing of particles

In Example 1, methyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (methyl 3- ) propionate) was used as a carrier particle.

Example  7: carrier  Manufacturing of particles

Except that 0.50 g of methyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate was used in place of BHT as an antioxidant in Example 1 to prepare carrier particles Respectively.

Example  8: carrier  Manufacturing of particles

Except that 0.75 g of methyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate was used in place of BHT as an antioxidant in Example 1 to prepare carrier particles Respectively.

Example  9: carrier  Manufacturing of particles

0.29 g of 2,2-methylenebis (4-methyl-6-tert-butylphenol) was used instead of BHT as the antioxidant in Example 1 , Carrier particles were prepared.

Example  10: carrier  Manufacturing of particles

Carrier particles were prepared in the same manner as in Example 1 except that 0.57 g of 2,2-methylenebis (4-methyl-6-tert-butylphenol) was used instead of BHT as an antioxidant in Example 1.

Example  11: carrier  Manufacturing of particles

Carrier particles were prepared in the same manner as in Example 1 except that 0.85 g of 2,2-methylenebis (4-methyl-6-tert-butylphenol) was used instead of BHT as an antioxidant in Example 1.

Example  12: carrier  Manufacturing of particles

Carrier particles were prepared in the same manner as in Example 1, except that the content of ethanol was adjusted to 23.55 mL in Example 1.

Example  13: carrier  Manufacturing of particles

Carrier particles were prepared in the same manner as in Example 1 except that the content of ethanol in Example 1 was adjusted to 27.47 mL.

Example  14: carrier  Manufacturing of particles

Carrier particles were prepared in the same manner as in Example 1, except that the content of ethanol was adjusted to 31.39 mL in Example 1.

Example  15: carrier  Manufacturing of particles

Carrier particles were prepared in the same manner as in Example 1, except that the content of ethanol in Example 1 was adjusted to 34.34 mL.

Example  16: carrier  Manufacturing of particles

Carrier particles were prepared in the same manner as in Example 1, except that the content of the antioxidant (BHT) was adjusted to 0.56 g and the content of ethanol was adjusted to 34.34 mL.

Example  17: carrier  Manufacturing of particles

1.98 g of pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] was used instead of BHT as an antioxidant in Example 1, and the content of ethanol was adjusted to 34.34 mL Carrier particles were prepared in the same manner as in Example 1. The results are shown in Table 1.

Example  18: carrier  Manufacturing of particles

Except that 0.75 g of methyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate was used instead of BHT as an antioxidant in Example 1 and the content of ethanol was adjusted to 34.34 mL Carrier particles were prepared in the same manner as in Example 1.

Example  19: carrier  Manufacturing of particles

The same procedure as in Example 1 was carried out except that 0.85 g of 2,2-methylenebis (4-methyl-6-tert-butylphenol) was used instead of BHT as the antioxidant in Example 1 and the content of ethanol was adjusted to 34.34 mL To prepare carrier particles.

Example  20: carrier  Manufacturing of particles

Carrier particles were prepared in the same manner as in Example 1 except that 250 mL of oil (8.8 cSt, 40 캜) was used in Example 1.

Example  21: carrier  Manufacturing of particles

Carrier particles were prepared in the same manner as in Example 1 except that 250 mL of the oil (50.0 cSt, 40 DEG C) was used in Example 1.

Example  22: carrier  Manufacturing of particles

Carrier particles were prepared in the same manner as in Example 1 except that 250 mL of the oil (100.0 cSt, 40 DEG C) was used in Example 1.

Example  23: carrier  Manufacturing of particles

Carrier particles were prepared in the same manner as in Example 1, except that the homogeneous solution in which the magnesium compound in the first reactor completely dissolved in Example 1 was stirred at a rotation speed of 700 rpm for 30 minutes.

Example  24: carrier  Manufacturing of particles

Carrier particles were prepared in the same manner as in Example 1, except that the homogeneous solution in which the magnesium compound in the first reactor completely dissolved in Example 1 was stirred at a rotation speed of 2200 rpm for 30 minutes.

Comparative Example  One: carrier  Manufacturing of particles

Carrier particles were prepared in the same manner as in Example 1, except that the antioxidant BHT was not added.

Comparative Example  2: carrier  Manufacturing of particles

Carrier particles were prepared in the same manner as in Example 1, except that the content of the antioxidant BHT was adjusted to 18.49 g in Example 1.

Comparative Example  3: carrier  Manufacturing of particles

Carrier particles were prepared in the same manner as in Example 1, except that the content of the antioxidant BHT in Example 1 was adjusted to 0.019 g.

Test Example  One: carrier  Evaluation of Particles

The shapes of the carrier particles prepared according to the above Examples and Comparative Examples were observed with an electron microscope (SEM: Scanning Electron Microscope) and are shown in Table 1.

Further, the particle size of the carrier particles suspended in hexane was measured with a laser particle analyzer (Mastersizer X, manufactured by Malvern Instruments) by a light transmission method. As a result, a cumulative distribution of the particle size was obtained, and the average particle size, the particle size distribution index and the fine particle content of the particles were obtained as follows.

(One) Average particle size (D ₅₀ ): the particle size corresponding to the cumulative weight of 50%

(2) Particle size distribution index (P): P = (D ₉₀ -D ₁₀ ) / D ₅₀

In the above, D ₉₀ is the particle size corresponding to the cumulative weight of 90%, and D ₁₀ is the particle size corresponding to the cumulative weight 10%

(3) Fine particle content: Cumulative weight% of particles having a particle diameter of less than 10 [

The shape of the carrier particle Average particle diameter [占 퐉] Particle size distribution index Fine particle content [wt%] Example 1 rectangle 62 1.15 5.6 Example 2 rectangle 47 1.25 2.6 Example 3 rectangle 74 1.55 2.7 Example 4 rectangle 44 1.25 4.2 Example 5 rectangle 56 1.24 3.2 Example 6 rectangle 80 1.25 5.3 Example 7 rectangle 41 1.66 2.7 Example 8 rectangle 48 1.69 3.4 Example 9 rectangle 57 1.52 4.9 Example 10 rectangle 51 1.36 2.8 Example 11 rectangle 49 1.47 3.8 Example 12 rectangle 48 1.67 7.5 Example 13 rectangle 60 1.14 5.9 Example 14 rectangle 56 1.17 6.1 Example 15 rectangle 47 1.25 7.9 Example 16 rectangle 49 1.55 7.9 Example 17 rectangle 85 1.55 6.0 Example 18 rectangle 58 1.06 8.2 Example 19 rectangle 59 1.21 6.3 Example 20 rectangle 52 1.26 4.9 Example 21 rectangle 44 1.44 3.6 Example 22 rectangle 38 1.17 2.7 Example 23 rectangle 61 1.55 4.9 Example 24 rectangle 46 1.42 3.8 Comparative Example 1 rectangle 49 1.57 3.8 Comparative Example 2 Large particles that do not coexist with spherical particles 135 3.62 4.7 Comparative Example 3 rectangle 56 2.01 4.15

Example  25: Preparation of catalyst

A 500 mL pressure-resistant glass reactor equipped with a stirrer and an oil circulation heater was sufficiently ventilated with nitrogen. TiCl ₄ was added to the reactor under nitrogen reflux and the reactor temperature was lowered to -20 ° C.

On the other hand, 13 g of carrier particles prepared in Example 1 were placed in 20 mL of decane at -10 캜 to prepare a low-temperature mixture. This low temperature mixture was added to the reactor, stirred for 60 minutes at a rotation speed of 200 rpm, and the temperature of the reactor was raised to 20 DEG C at a rate of 0.25 DEG C / min. When the temperature of the reactor reached 20 캜, the reactor was agitated at a rotation speed of 200 rpm for 30 minutes, and then the temperature of the reactor was raised to 100 캜 at a rate of 1 캜 / minute. When the temperature of the reactor reached 100 ° C, C-donor (0.01 / MgCl ₂ mol / mol) was added.

Thereafter, the temperature of the reactor was raised to 120 ° C. while maintaining the temperature of the reactor at 100 ° C., TiCl ₄ was removed from the reactor, TiCl ₄ was added thereto, and the mixture was maintained at the same temperature for about 1 hour. This method was repeated twice.

Thereafter, the temperature of the reactor was lowered to 70 ° C, the TiCl ₄ was removed again, the purified hexane was added thereto, and the resulting catalyst was stirred for about 1 hour to wash the resulting catalyst. This washing operation was repeated six times in total. After the removal of the remaining TiCl ₄ , the produced catalyst was ventilated under nitrogen flow for 2 to 4 hours and dried to obtain a catalyst. The shape of the prepared catalyst was spherical, and the particle size ranged from about 40 to 70 mu m.

Comparative Example  4: Preparation of catalyst

A catalyst was prepared in the same manner as in Example 25 except that the carrier particles prepared according to Comparative Example 1 were used in Example 25.

Comparative Example  5: Preparation of catalyst

A catalyst was prepared in the same manner as in Example 25 except that the carrier particles prepared in Comparative Example 2 were used in Example 25.

Comparative Example  6: Preparation of catalyst

A catalyst was prepared in the same manner as in Example 25 except that the carrier particles prepared in Example 25 and Comparative Example 3 were used.

Example  26: Manufacture of polypropylene

First, a 1 L high-pressure reactor heated to 120 占 폚 was evacuated with nitrogen for 1 hour to fill the high-pressure reactor with nitrogen. The autoclave reactor was then filled with propylene by lowering the temperature of the autoclave to 25 DEG C and ventilating with propylene. Triethylaluminum (TEAL) diluted in a decane solvent at a molar concentration of 1 mol was introduced into the high-pressure reactor, and cyclohexylmethyldimethoxysilane (external electron donor) diluted in a decane solvent was added to a Si / Ti molar ratio of 30 Respectively.

On the other hand, a solution prepared in advance by diluting the catalyst prepared in Example 25 with decane solvent was prepared. Then, the catalyst diluted in the decane solvent was added to the high-pressure reactor in an amount of 0.005 g based on Ti, hydrogen and propylene were added thereto in sequence, and the mixture was stirred to carry out prepolymerization.

After the prepolymerization, the temperature of the high-pressure reactor was raised to 70 ° C. and the polymerization was carried out at 70 ° C. for 1 hour. Unreacted propylene was discharged to the atmosphere and the temperature of the high-pressure reactor was lowered to room temperature. The resulting polypropylene was dried in a vacuum oven at 50 DEG C for 10 hours.

Comparative Example  7: Preparation of polypropylene

A polypropylene was prepared in the same manner as in Example 26 except that the catalyst prepared in Example 26 in accordance with Comparative Example 4 was used.

Comparative Example  8: Preparation of polypropylene

A polypropylene was prepared in the same manner as in Example 26 except that the catalyst prepared in Example 26 in accordance with Comparative Example 5 was used.

Comparative Example  9: Preparation of polypropylene

A polypropylene was prepared in the same manner as in Example 26 except that the catalyst prepared in Example 26 in accordance with Comparative Example 6 was used.

Test Example  2: Evaluation of physical properties of catalyst

The particle size of the catalyst suspended in hexane was measured by a laser particle analyzer (Mastersizer X (manufactured by Malvern Instruments)) by a light transmission method. As a result, a cumulative distribution of the particle size was obtained, and the particle size corresponding to the cumulative weight of 50% was defined as the average particle size (D ₅₀ ). The average particle diameters of the catalysts used in Example 26 and Comparative Example 8 were determined by these methods and are shown in Table 2.

Further, the catalyst activity values defined by the weight of the catalyst added in the polymerization process according to Example 26 and Comparative Example 8 and the amount of the polymer produced per 1 g of the catalyst through the weight of the polymer obtained using this amount of catalyst were obtained Are shown in Table 2 below.

Catalytic activity [kg-PP / g-Cat.] Average particle diameter [占 퐉] Example 26 43 51 Comparative Example 8 10 123

Referring to Table 2, it is confirmed that when the carrier particles contain an excessive amount of an antioxidant (see Comparative Example 2), the carrier particles have a low sphericity and a very large average particle diameter and poor catalytic activity. On the contrary, it is confirmed that when the carrier particles contain an appropriate level of antioxidant, it is possible to provide a catalyst having a proper particle size and exhibiting high catalytic activity.

Example  27: Molding of polypropylene

The polypropylene powder polymerized in Example 26 was melted at a temperature of 200 캜 using a mill or a twin-screw extruder and then extruded at a temperature of 230 캜 to obtain pellets.

Comparative Example  10: Molding of polypropylene

Pellets were obtained in the same manner as in Example 27, except that the polypropylene powder polymerized in Comparative Example 7 was used in Example 27.

Comparative Example  11: Molding of polypropylene

Pellets were obtained in the same manner as in Example 27 except that the polypropylene powder polymerized in Example 27 in Comparative Example 9 was used.

Test Example  3: Property evaluation of polypropylene

30 g of the pellets prepared in Example 27 and Comparative Examples 10 and 11 were removed from the air and put into a Colorimeter Model SA-2000, and the color b value of the pellet was measured 10 times to obtain an average value. In the L ^* a ^* b ^* color coordinate system defined by the International Commission on Illumination (CIE), color b represents a color that is biased towards yellow if positive and negative toward blue.

Yellowness index Example 27 1.1 Comparative Example 10 3.9 Comparative Example 11 3.4

Referring to Table 3, when carrier particles not containing an antioxidant were used (corresponding to Comparative Example 10), or carrier particles containing a very small amount of an antioxidant were used (corresponding to Comparative Example 11) It is confirmed that the resin is oxidized and discolored due to high heat in the molding process. On the contrary, according to one embodiment of the present invention, it is confirmed that when a carrier particle containing an appropriate amount of antioxidant is used, a molded article can be provided without discoloration without using an antioxidant in a polymerization process and a molding process.

Claims (7)

Wherein the homogeneous solution is prepared by cooling a homogeneous solution of an oil, a magnesium halide, an alcohol having 1 to 5 carbon atoms and an antioxidant in the presence of a hydrocarbon solvent having 6 or more carbon atoms, and containing 1 to 50 mmol of an antioxidant per 1 mol of magnesium atom Carrier particles represented by:
(2)
MgX _m (ROH) _z (AO) _{(6- (m + z))}
M is an integer of 0 to 2, z is an integer of 1 to 6, and the sum of m + z is 3 (wherein R < 3 > is an alkyl group having 1 to 5 carbon atoms; AO is an antioxidant; Lt; / RTI >
The carrier particle according to claim 1, wherein the carrier particle comprises a compound having a structure represented by the following formula (1) as the antioxidant:
[Chemical Formula 1]

In Formula 1,
n is an integer of 1 to 4,
R is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 35 carbon atoms, An alkylaryl group having 7 to 35 carbon atoms, an arylalkenyl group having 8 to 40 carbon atoms, a heteroaryl group having 5 to 30 carbon atoms, an arylamine group having 6 to 30 carbon atoms, a heteroarylamine group having 5 to 30 carbon atoms, Is an alkyl group having 1 to 5 carbon atoms bonded through the intermediacy of -O-, -S-, -CONH-, -COO- or -OCO-,
When n is an integer of 2 to 4, a plurality of Rs may be the same or different, and a carbon which is not substituted with R is bonded to hydrogen.
3. The antioxidant according to claim 2, wherein the antioxidant is an antioxidant, wherein n is 2 and R are the same or different from each other and each independently represents a methyl group, ethyl group, n-propyl group, isopropyl group, n- Butyl group, or tert-butyl group.
The antioxidant according to claim 1, wherein the antioxidant is 2,6-di-tert-butyl-4-methylphenol (BHT), pentaerythritol tetrakis [3- Butyl-4-hydroxyphenyl) propionate]), methyl 3- (3,5-di-tert- Di-tert-butyl-4-hydroxyphenyl) propionate, 2,2-methylenebis (4- Methyl-6-tert-butylphenol), stearyl-? - (3,5-di-tert-butyl-4-hydroxyphenyl) Butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert- butyl 3,5-di-tert-butyl-4-hydroxybenzyl) benzene), 3,5-bis (1, 1-dimethylethyl) -4-hydroxybenzenepropionic acid thio-2,1-ethanediyl ester (3,5-bis (1,1-dimethylethyl) -4-hydroxybenzenepropanoic (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide] (N, N'- Propane-1,3-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide], 4-hydroxy-3,5-di- (3,5-di-tert-butylphenylpropionic acid), 1,1-bis (3,5-di- -tert-butyl-2-hydroxyphenyl) ethane, 4,4'-methylenebis (2,6-di-tert-butylphenol) , Triethylene glycol bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, Bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl) hydrazine, 1,2-bis Bis (6-tert-butyl-p-cresol), diethyl 3,5-di-tert-butyl-4-hydroxybenzyl Diethyl tert-butyl-4-hydroxybenzyl phosphate and 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert- ) Benzene (1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene).
The carrier particle according to claim 1, wherein the average particle diameter (D ₅₀ ) is 35 to 90 탆 and the particle size distribution index is 1.00 to 1.80.
delete The carrier particle for a propylene polymerization catalyst according to claim 1,