KR100572616B1 - A solid catalyst for olefin polymerization and a method for preparing the same - Google Patents

Abstract

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid catalyst for olefin polymerization and a method for preparing the same, and more particularly, to a highly active olefin polymerization, particularly a propylene polymerization solid, containing an environmentally friendly non-aromatic monoalkoxy monoester compound as an electron donor. And a method for producing the same. Using the catalyst according to the present invention, polymers having high stereoregularity and high melt flow index can be produced in high yield without any concern for environmental hormones.

Olefin, polymerization, catalyst, preparation method, non-aromatic, monoalkoxy monoester

Description

Solid catalyst for olefin polymerization and its manufacturing method {A SOLID CATALYST FOR OLEFIN POLYMERIZATION AND A METHOD FOR PREPARING THE SAME}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid catalyst for olefin polymerization and a method for preparing the same, and more particularly, to a highly active olefin polymerization, particularly a propylene polymerization solid, containing an environmentally friendly non-aromatic monoalkoxy monoester compound as an electron donor. And a method for producing the same.

Until now, many catalysts for propylene polymerization and polymerization methods using the same have been reported. In particular, in order to lower the cost by increasing the catalytic activity, and improve the physical properties of the polymer by improving the catalytic performance such as stereoregularity, the use of diesters of aromatic dicarboxylic acid as the internal electron donor is a widely known method For example, a number of patents have been filed, such as US Patent No. 4,562,173, US Patent No. 4,981,930, Korean Patent No. 072844, and the like. The exemplary patents disclose methods for preparing catalysts that are highly active and express high stereoregularity by using aromatic dialkyldiesters or aromatic monoalkylmonoesters.

However, diester compounds of aromatic dicarboxylic acids cause serious problems as environmental hormone substances which, even in very small amounts, can have significant effects on reproductive function, growth disorders, malformations, cancer, etc. in ecosystems and humans. can do. Therefore, there has been a recent demand for the use of catalysts containing environmentally friendly substances other than environmental hormones as internal electron donors in the production of polypropylene for use in food packaging containers and the like.

Meanwhile, Korean Patent Laid-Open Publication No. 1999-008107 discloses a method for preparing a catalyst using a non-aromatic 1,3-diether compound as an internal electron donor, but this is still not satisfactory in view of polymerization activity and stereoregularity of the resultant polymer. As a result, there is a need for an improved catalyst for olefin polymerization using a non-aromatic internal electron donor and a method of preparing the same.

The present invention is to solve the problems of the prior art as described above, an object of the present invention is an olefin, especially propylene polymerization, exhibiting high polymerization activity without containing a diester compound of an aromatic dicarboxylic acid which is an environmental hormone substance It is to provide a solid catalyst and a method for producing the same, and by using the catalyst according to the present invention, a polymer having high stereoregularity and high melt flow index can be produced in high yield without any concern for environmental hormones. .

According to the present invention, there is provided a solid titanium catalyst for olefin polymerization containing a non-aromatic monoalkoxy monoester compound represented by the following formula (I) as an internal electron donor:

In the above, R ₁ , R ₂ , R ₃ and R ₄ are each an alkyl group of 1 to 10 carbon atoms, may be the same or different from each other.

As the non-aromatic monoalkoxy monoester compound contained in the solid titanium catalyst for olefin polymerization according to the present invention, in particular, CH ₃ OC (O) C (CH (CH ₃ ) CH ₂ CH ₃ ) ₂ CH ₂ OCH ₃ , C ₂ H ₅ OC (O) C (CH (CH ₃ ) CH ₂ CH ₃ ) ₂ CH ₂ OCH ₃ , CH ₃ OC (O) C (CH (CH ₃ ) CH ₂ CH ₃ ) ₂ CH ₂ OC ₂ H ₅ , C ₂ H ₅ OC (O) C (CH (CH ₃ ) CH ₂ CH ₃ ) ₂ CH ₂ OC ₂ H ₅ , CH ₃ OC (O) C (CH (CH ₃ ) CH ₃ ) ₂ CH ₂ OCH ₃ , C ₂ H ₅ OC (O) C (CH (CH ₃ ) CH ₃ ) ₂ CH ₂ OCH ₃ , CH ₃ OC (O) C (CH (CH ₃ ) CH ₃ ) ₂ CH ₂ OC ₂ H ₅ and It is preferable to use a compound selected from the group consisting of C ₂ H ₅ OC (O) C (CH (CH ₃ ) CH ₃ ) ₂ CH ₂ OC ₂ H ₅ .

In addition, according to the present invention, (1) the first step of reacting dialkoxy magnesium with a transition metal halide compound in the presence of an organic solvent at 0 ~ 100 ℃; (2) While the temperature of the resultant of step (1) is gradually raised to the maximum temperature of 80 to 130 ° C, the non-aromatic monoalkoxy monoester compound represented by the following formula (I) is added thereto at least once for reaction. step:

In the above, R ₁ , R ₂ , R ₃ and R ₄ are each an alkyl group of 1 to 10 carbon atoms, and may be the same or different from each other; And (3) reacting the resultant of step (2) with the transition metal halide compound at 80 to 130 ° C. in a second manner.

In the catalyst preparation method according to the present invention, as the organic solvent used in the step (1), an aliphatic or aromatic hydrocarbon having 6 to 12 carbon atoms, preferably 7 to 10 carbon atoms, may be used. Heptane, octane, nonane, decane, toluene, xylene and the like.

In the catalyst preparation method according to the present invention, the dialkoxy magnesium used in the step (1) may be obtained by reacting magnesium metal in a particulate state (average particle size of 50 to 200 μm) with anhydrous alcohol in the presence of magnesium chloride. have.

In the catalyst production method according to the present invention, as the transition metal halide compound used in the step (1), halide compounds of the Group IV transition metal of the periodic table are preferably used, and more preferably Ti (OR) _a. Titanium halide compounds represented by the general formula of X _4-a are used. In the general formula of the titanium halide compound, R is an alkyl group having 1 to 10 carbon atoms, X is a halogen element, and a is an integer of 0 to 3 to match the valence of the general formula.

In the catalyst preparation method according to the present invention, the contact reaction between the dialkoxy magnesium and the transition metal halide compound in the step (1) is carried out at 0 ~ 100 ℃, preferably at a temperature of 5 ~ 50 ℃. At this time, if the temperature of the contact reaction is less than 0 ° C, the reaction is less likely to occur smoothly, and if it exceeds 100 ° C, it is difficult to control the shape and size of the catalyst particles. In addition, the amount of the transition metal halide compound used in step (1) is preferably 0.1 to 10 moles, more preferably 0.3 to 2 moles per 1 mole of dialkoxymagnesium, and the polymerization activity and physical properties of the catalyst prepared. It is preferable in terms of.

In the catalyst preparation method according to the present invention, the non-aromatic monoalkoxy monoester compound used in step (2) is the same as the non-aromatic monoalkoxy monoester compound contained in the catalyst according to the present invention described above. Thus, for example, CH ₃ OC (O) C (CH (CH ₃ ) CH ₂ CH ₃ ) ₂ CH ₂ OCH ₃ , C ₂ H ₅ OC (O) C (CH (CH ₃ ) CH ₂ CH ₃ ) ₂ CH ₂ OCH ₃ , CH ₃ OC (O) C (CH (CH ₃ ) CH ₂ CH ₃ ) ₂ CH ₂ OC ₂ H ₅ , C ₂ H ₅ OC (O) C (CH (CH ₃ ) CH ₂ CH ₃ ) ₂ CH ₂ OC ₂ H ₅ , CH ₃ OC (O) C (CH (CH ₃ ) CH ₃ ) ₂ CH ₂ OCH ₃ , C ₂ H ₅ OC (O) C (CH (CH ₃ ) CH ₃ ) ₂ CH ₂ OCH ₃ , CH ₃ OC (O) C (CH (CH ₃ ) CH ₃ ) ₂ CH ₂ OC ₂ H ₅ , C ₂ H ₅ OC (O) C (CH (CH ₃ ) CH ₃ ) ₂ CH It is preferable to use compounds in which R ₁ , R ₂ , R ₃ and R ₄ are the same as or different alkyl groups having 1 to 4 carbon atoms in formula (I), such as ₂ OC ₂ H ₅ and the like.

In the catalyst production method according to the present invention, the addition of the non-aromatic monoalkoxy monoester compound in the step (2), while gradually raising the temperature of the resultant of the step (1) to the maximum temperature of 80 ~ 130 ℃ At least once. When the addition of the non-aromatic monoalkoxy monoester compound is completed, the reaction is performed for a predetermined time within the range of the elevated temperature. If the temperature is less than 80 ° C., the reaction is difficult to complete to a sufficient degree, and if it exceeds 130 ° C., the polymerization activity of the catalyst prepared by activating an unwanted side reaction decreases, and the resulting stereoregularity of the resulting polymer is produced. Can be bad. In addition, the non-aromatic monoalkoxy monoester compound is preferably at least once, preferably at least twice, in view of the efficiency of catalyst production. The total amount of the non-aromatic monoalkoxy monoester compound used in the step (2) is preferably 0.1 to 1.0 parts by weight based on 1 part by weight of the dialkoxy magnesium. When the total amount of the non-aromatic monoalkoxy monoester compound is out of this range, the polymerization activity of the catalyst to be produced may be lowered, and the stereoregularity of the resulting polymer may be worsened.

In the catalyst production method according to the present invention, in the step (3), by reacting the resultant of the step (2) with the transition metal halide compound at 80 ~ 130 ℃ secondary, it is possible to increase the polymerization activity of the catalyst. The kind of the transition metal halide compound which can be preferably used in step (3) is the same as the kind of the preferred transition metal halide compound mentioned in step (1). As in the present invention, when the transition metal halide compound is added to the low temperature and high temperature stages at the time of preparation of the catalyst, the production yield of the catalyst and the polymerization activity of the catalyst to be produced can be increased, and also preferable for controlling the particle shape of the catalyst. .

In the method for preparing a catalyst according to the present invention, in addition to the non-aromatic monoalkoxy monoester compound, an electron donor compound commonly used in the preparation of a solid catalyst for olefin polymerization can be additionally used as an internal electron donor, and among them, a non-aromatic compound It is preferable to use additionally.

In the catalyst production method according to the present invention, the reactions of the above steps are preferably carried out in a reactor equipped with a stirrer, in which a nitrogen gas atmosphere is sufficiently removed from the water.

The catalyst prepared as described above is in the form of a mixed slurry, which is finally washed with an organic solvent and dried to obtain a solid catalyst for olefin polymerization.

The content of each component included in the solid catalyst provided according to the present invention is not specifically defined, but is 15 to 25% by weight of magnesium, 1 to 5% by weight of titanium, 5 to 15% by weight of internal electron donor, and 50 to halogen atoms. It is preferable that it is 70 weight%.

The solid catalyst component provided according to the present invention may be used by prepolymerization with ethylene or α-olefin before being used as a catalyst for the polymerization reaction. The prepolymerization reaction can be carried out at sufficiently low temperatures and ethylene or α-olefin pressure conditions in the presence of a hydrocarbon solvent such as hexane, the solid catalyst component and an organoaluminum compound such as triethylaluminum. The prepolymerization helps to improve the shape of the final polymer after the main polymerization by maintaining the catalyst shape by surrounding the catalyst particles with the prepolymer. The preferred weight ratio of prepolymer / catalyst after prepolymerization is about 0.1: 1 to 20: 1.

 Hereinafter, the present invention will be described in more detail with reference to the following examples. However, these examples are for illustrative purposes only, and the present invention is not limited by these examples.

Example 1

[Production of Solid Catalyst]

In a glass reactor equipped with a 1 liter stirrer sufficiently substituted with nitrogen, 150 ml of toluene and 25 g of diethoxy magnesium (spherical with an average particle diameter of 60 µm, having a particle size distribution index of 0.86 and an apparent density of 0.32 g / cc) were used. The temperature was kept at 10 ° C. After diluting 25 ml of titanium tetrachloride in 50 ml of toluene and injecting it over 1 hour, the temperature of the reactor was heated up to 30 degreeC at a speed | rate of 0.5 degreeC per minute. The reaction mixture was held at 30 ° C. for 1 hour, then 2.5 ml of C ₂ H ₅ OC (O) C (CH (CH ₃ ) CH ₂ CH ₃ ) ₂ CH ₂ OCH ₃ was injected and again at a rate of 0.5 ° C. per minute. The temperature was raised to 110 ° C. During the temperature increase, 2.5 ml of C ₂ H ₅ OC (O) C (CH (CH ₃ ) CH ₂ CH ₃ ) ₂ CH ₂ OCH ₃ was additionally injected at 40 ° C. and 60 ° C., respectively.

The reaction mixture was kept at 110 ° C. for 1 hour, then the temperature was lowered to 90 ° C., then stirring was stopped, the supernatant was removed and washed once with 200 ml of toluene. 150 ml of toluene and 50 ml of titanium tetrachloride were further added thereto, and the temperature was raised to 110 ° C. and maintained for 1 hour. After the reaction was completed, the resultant slurry mixture was washed twice with 200 ml of toluene each time, and washed five times with 200 ml of normal hexane each time at 40 ° C. to obtain a pale yellow solid catalyst component. The titanium content in the solid catalyst component obtained by drying for 18 hours in flowing nitrogen was 2.87 wt%.

[Propylene polymerization]

After mounting a small glass tube filled with 5 mg of the catalyst prepared above in a 2 liter high pressure stainless reactor, the reactor was sufficiently replaced with nitrogen. 3 mmol of triethylaluminum and 0.30 mmol of dicyclopentyldimethoxysilane were charged to the reactor. Subsequently, 1000 ml of hydrogen and 1.2 L of propylene in the liquid state were sequentially added, and the reactor temperature was raised to 70 ° C. and the stirrer was operated. The polymerization was started by breaking the glass tube mounted therein by the operation of the stirrer. After 1 hour from the start of the polymerization, the temperature of the reactor was lowered to room temperature, and the polymerization reaction was terminated by opening the discharge valve to completely discharge the propylene in the reactor.

For the obtained polymer, catalytic activity, stereoregularity and melt flow index were determined in the following manner, and the results are shown in Table 1.

① Catalytic Activity (kg-PP / g-cat): Polymer Production (kg) / Catalyst (g)

② Stereoregularity (X.I.): weight% of insoluble component precipitated after crystallization in boiling xylene for one hour

③ Melt Flow Index (MFR) (g / 10min): measured at 230 ℃, 2.16kg load by ASTM1238

Example 2

A solid catalyst was prepared in the same manner as in Example 1, except that 0.30 mmol of cyclohexylmethyldimethoxysilane was used instead of 0.30 mmol of dicyclopentyldimethoxysilane in the above [propylene polymerization]. Propylene polymerization was carried out.

For the obtained polymer, catalytic activity, stereoregularity and melt flow index were determined in the same manner as in Example 1, and the results are shown in Table 1.

Example 3

In [Preparation of solid catalyst], CH ₃ OC (O) C (CH (CH ₃ ) CH instead of C ₂ H ₅ OC (O) C (CH (CH ₃ ) CH ₂ CH ₃ ) ₂ CH ₂ OCH _{3. A} solid catalyst was prepared in the same manner as in Example 1, except that ₂ CH ₃ ) ₂ CH ₂ OCH ₃ was used, and propylene polymerization was performed in the same manner as in Example 1.

For the obtained polymer, catalytic activity, stereoregularity and melt flow index were determined in the same manner as in Example 1, and the results are shown in Table 1.

Example 4

In [Preparation of solid catalyst], C ₂ H ₅ OC (O) C (CH (CH ₃ ) CH ₂ CH ₃ ) ₂ CH ₂ OCH ₃ instead of C ₂ H ₅ OC (O) C (CH (CH ₃ A solid catalyst was prepared in the same manner as in Example 1, except that) CH ₂ CH ₃ ) ₂ CH ₂ OC ₂ H ₅ was used, and propylene polymerization was performed in the same manner as in Example 1.

For the obtained polymer, catalytic activity, stereoregularity and melt flow index were determined in the same manner as in Example 1, and the results are shown in Table 1.

Example 5

In [Preparation of solid catalyst], CH ₃ OC (O) C (CH (CH ₃ ) CH instead of C ₂ H ₅ OC (O) C (CH (CH ₃ ) CH ₂ CH ₃ ) ₂ CH ₂ OCH _{3. A} solid catalyst was prepared in the same manner as in Example 1, except that ₂ CH ₃ ) ₂ CH ₂ OC ₂ H ₅ was used, and propylene polymerization was performed in the same manner as in Example 1.

For the obtained polymer, catalytic activity, stereoregularity and melt flow index were determined in the same manner as in Example 1, and the results are shown in Table 1.

Example 6

In [Preparation of solid catalyst], C ₂ H ₅ OC (O) C (CH (CH ₃ ) CH ₂ CH ₃ ) ₂ CH ₂ OCH ₃ instead of C ₂ H ₅ OC (O) C (CH (CH ₃ A solid catalyst was prepared in the same manner as in Example 1, except that) CH ₃ ) ₂ CH ₂ OCH ₃ was used, and propylene polymerization was performed in the same manner as in Example 1.

For the obtained polymer, catalytic activity, stereoregularity and melt flow index were determined in the same manner as in Example 1, and the results are shown in Table 1.

Example 7

In [Preparation of Solid Catalyst], C ₂ H ₅ OC (O) C (CH (CH ₃ ) CH ₂ CH ₃ ) ₂ CH ₂ OCH ₃ was added at 30 ° C., 40 ° C. and 60 ° C. at 1.5 ° C. instead of 2.5 mL. Except that each was injected, a solid catalyst was prepared in the same manner as in Example 1, and propylene polymerization was carried out in the same manner as in Example 1 using the same.

For the obtained polymer, catalytic activity, stereoregularity and melt flow index were determined in the same manner as in Example 1, and the results are shown in Table 1.

Example 8

In [Preparation of Solid Catalyst], C ₂ H ₅ OC (O) C (CH (CH ₃ ) CH ₂ CH ₃ ) ₂ CH ₂ OCH ₃ was added at 30 ° C., 40 ° C. and 60 ° C. in 3.5 ml increments instead of 2.5 ml. Except that each was injected, a solid catalyst was prepared in the same manner as in Example 1, and propylene polymerization was carried out in the same manner as in Example 1 using the same.

For the obtained polymer, catalytic activity, stereoregularity and melt flow index were determined in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 1

In [Production of solid catalyst], except that diisobutyl phthalate, which is an aromatic compound, was used instead of C ₂ H ₅ OC (O) C (CH (CH ₃ ) CH ₂ CH ₃ ) ₂ CH ₂ OCH ₃ , A solid catalyst was prepared in the same manner as in Example 1, and propylene polymerization was performed in the same manner as in Example 1.

For the obtained polymer, catalytic activity, stereoregularity and melt flow index were determined in the same manner as in Example 1, and the results are shown in Table 1.

TABLE 1

Catalytic activity (kg-PP / g-cat) Stereoregularity (X.I.) (% by weight) Melt Flow Index (MFR) (g / 10min) Example 1 32 96.0 13.5 Example 2 28 93.4 33.3 Example 3 29 95.8 14.8 Example 4 30 96.5 11.9 Example 5 30 96.0 14.2 Example 5 28 96.4 12.3 Example 7 35 95.7 15.3 Example 8 30 96.9 10.9 Comparative Example 1 27 98.2 4.2

As can be seen from Table 1, when the solid catalyst component for olefin polymerization according to the present invention is used for the polymerization of propylene, polymers having excellent stereoregularity and melt flow index without any concern about containing environmental hormones are obtained. It can be obtained in high yield.

As described above, according to the present invention, it is possible to obtain a solid catalyst component for olefin polymerization that does not contain any aromatic ester compound which is an environmental hormone, and the polymer prepared using the polymer has excellent stereoregularity and melt flow index. In addition, since it does not contain any environmental hormones, it can be suitably used for applications such as food packaging materials.

Claims (6)

Solid titanium catalyst for olefin polymerization containing the non-aromatic monoalkoxy monoester compound represented by following formula (I) as an internal electron donor:

In the above, R ₁ , R ₂ , R ₃ and R ₄ are each an alkyl group of 1 to 10 carbon atoms, may be the same or different from each other. The method of claim 1, wherein the non-aromatic monoalkoxy monoester compound, CH ₃ OC (O) C (CH (CH ₃ ) CH ₂ CH ₃ ) ₂ CH ₂ OCH ₃ , C ₂ H ₅ OC (O) C ( CH (CH ₃ ) CH ₂ CH ₃ ) ₂ CH ₂ OCH ₃ , CH ₃ OC (O) C (CH (CH ₃ ) CH ₂ CH ₃ ) ₂ CH ₂ OC ₂ H ₅ , C ₂ H ₅ OC (O) C (CH (CH ₃ ) CH ₂ CH ₃ ) ₂ CH ₂ OC ₂ H ₅ , CH ₃ OC (O) C (CH (CH ₃ ) CH ₃ ) ₂ CH ₂ OCH ₃ , C ₂ H ₅ OC (O) C (CH (CH ₃ ) CH ₃ ) ₂ CH ₂ OCH ₃ , CH ₃ OC (O) C (CH (CH ₃ ) CH ₃ ) ₂ CH ₂ OC ₂ H ₅ and C ₂ H ₅ OC (O) C ( CH (CH ₃ ) CH ₃ ) ₂ CH ₂ OC ₂ H ₅ Solid titanium catalyst for olefin polymerization, characterized in that selected from the group consisting of. (1) firstly reacting dialkoxy magnesium with a transition metal halide compound in the presence of an organic solvent at 0 to 100 ° C .; (2) While the temperature of the resultant of step (1) is gradually raised to the maximum temperature of 80 to 130 ° C, the non-aromatic monoalkoxy monoester compound represented by the following formula (I) is added thereto at least once for reaction. step:

In the above, R ₁ , R ₂ , R ₃ and R ₄ are each an alkyl group of 1 to 10 carbon atoms, and may be the same or different from each other; And (3) A method of producing a solid titanium catalyst for olefin polymerization comprising the step of reacting the resultant of step (2) with a transition metal halide compound at 80 to 130 ° C. in a second manner. The method of claim 3, wherein the transition metal halide compound is a titanium halide compound represented by the general formula of Ti (OR) _a X _4-a , wherein R is an alkyl group of 1 to 10 carbon atoms, X is a halogen element And a is an integer from 0 to 3, wherein the solid titanium catalyst for olefin polymerization. The non-aromatic monoalkoxy monoester compound according to claim 3, wherein the non-aromatic monoalkoxy monoester compound is selected from CH ₃ OC (O) C (CH (CH ₃ ) CH ₂ CH ₃ ) ₂ CH ₂ OCH ₃ , C ₂ H ₅ OC (O) C ( CH (CH ₃ ) CH ₂ CH ₃ ) ₂ CH ₂ OCH ₃ , CH ₃ OC (O) C (CH (CH ₃ ) CH ₂ CH ₃ ) ₂ CH ₂ OC ₂ H ₅ , C ₂ H ₅ OC (O) C (CH (CH ₃ ) CH ₂ CH ₃ ) ₂ CH ₂ OC ₂ H ₅ , CH ₃ OC (O) C (CH (CH ₃ ) CH ₃ ) ₂ CH ₂ OCH ₃ , C ₂ H ₅ OC (O) C (CH (CH ₃ ) CH ₃ ) ₂ CH ₂ OCH ₃ , CH ₃ OC (O) C (CH (CH ₃ ) CH ₃ ) ₂ CH ₂ OC ₂ H ₅ and C ₂ H ₅ OC (O) C ( CH (CH ₃ ) CH ₃ ) ₂ CH ₂ OC ₂ H _{5 A} method for producing a solid titanium catalyst for olefin polymerization, characterized in that selected from the group consisting of. The method for producing a solid titanium catalyst for olefin polymerization according to claim 3, wherein the total amount of the non-aromatic monoalkoxy monoester compound is 0.1 to 1.0 part by weight based on 1 part by weight of the dialkoxy magnesium.