KR101795317B1 - A solid catalyst for propylene polymerization and a method for preparation of polypropylene - Google Patents

Abstract

The present invention relates to a solid catalyst for propylene polymerization and to a method for manufacturing polypropylene using the same, and provides a solid catalyst composed of a carrier, titanium halide, an organic electron donor, and the like generated through reaction of dialkoxy magnesium with metal halide, and a method for manufacturing polypropylene using the same. Especially, by using an internal electron donor containing a carbonyl group and an alkoxy group among two types of organic electron donors used in the present invention, a solid catalyst system proposed in the present invention can be applied to various types of propylene polymerization processes such as slurry polymerization, bulk polymerization or gas phase polymerization, and the like, and can manufacture polypropylene excellent in high activity and stereoregularity.

Description

TECHNICAL FIELD [0001] The present invention relates to a solid catalyst for the polymerization of propylene, and a process for producing the same. BACKGROUND ART < RTI ID = 0.0 >

The present invention relates to a solid catalyst comprising a carrier formed by the reaction of a dialkoxy magnesium with a metal halide, a titanium halide, an organic electron donor and the like, and a method for producing a polypropylene using the solid catalyst, wherein a Ziegler- To produce a propylene polymer, a polypropylene resin having high stereoregularity can be produced with a high yield.

BACKGROUND ART Polypropylene is widely used as a material material, particularly in daily life goods such as food containers, and in automobiles and electronic products, in real life and commercially. For the performance of various polypropylene products, it is important to improve the rigidity through high crystallinity, and for this purpose, the role of polymerization catalyst is desperately required. That is, the design of the catalyst system must be accompanied to improve the stereoregularity of the resulting polymer. In addition, the higher the polymerization activity of the catalyst is, the more advantageous for economical efficiency in the production of the polymer.

On the other hand, the catalyst system used for gas phase polymerization, slurry polymerization and bulk polymerization of propylene is generally composed of a Ziegler-Natta catalyst component, alkyl aluminum and an external electron donor. Particularly, such a catalyst component is known as a solid catalyst containing magnesium, titanium, an internal electron donor and halogen as essential components, and it is known that the internal electron donor has a considerable influence on the activity and stereoregularity of the catalyst depending on the molecular structure have. It is a widely known method to use a diester of an aromatic dicarboxylic acid as an internal electron donor in order to lower the cost through the increase of the catalyst activity and to improve the property of the polymer by improving the catalytic performance such as stereoregularity, Patents related thereto were filed. U.S. Patent No. 4,562,173, U.S. Patent No. 4,981,930, and Korean Patent No. 0072844, for example, disclose the use of an aromatic dialkyl diester or an aromatic monoalkyl monoester to produce high activity, In the presence of a catalyst.

The methods of these patents are not sufficiently satisfactory to obtain a high stereoregular polymer in high yield and require improvement.

Korean Patent No. 0491387 discloses a non-aromatic diether material and Korean Patent No. 0572616 discloses a method of producing a catalyst using a nonaromatic but simultaneously having a ketone and an ether functional group as an internal electron donor. However, both of these methods need to be greatly improved in terms of both activity and stereoregularity.

U.S. Patent No. 2011/0040051 also discloses a method for preparing a catalyst by using a mixture of diethyl 2,3-diisopropyl-2-cyanosuccinate and 9,9-bismethoxyflorene as an internal electron donor However, it is very difficult to improve both in terms of activity and stereoregularity.

It is an object of the present invention to provide a solid catalyst capable of producing polypropylene having high stereoregularity and high activity and solving the problems of the prior art as described above and a process for producing polypropylene using the solid catalyst.

The method for producing a solid catalyst for propylene polymerization according to the present invention is characterized by comprising the following steps.

(1) reacting diethoxy magnesium with a metal halide compound in the presence of an organic solvent at a relatively low temperature;

(2) reacting two internal electron donors while raising the temperature after diethoxy magnesium reaction;

(3) reacting at a high temperature for a predetermined time;

(4) reacting with the metal halide compound at a high temperature in a second step and washing it.

In the process for producing a solid catalyst as described above, diethoxy magnesium used in the step (1) is a product obtained by reacting metallic magnesium with anhydrous alcohol in the presence of magnesium chloride and having an average particle size of 10 to 200 탆, If the average particle size is less than 10 탆, the fine particles of the prepared catalyst are undesirably increased. When the average particle size is more than 200 탆, the side view density And it is difficult to have a uniform particle shape in the production of the catalyst, which is not preferable.

The organic solvent used in the step (1) is not particularly limited and may be an aliphatic hydrocarbon having 6 to 12 carbon atoms, an aromatic hydrocarbon, a halogenated hydrocarbon or the like, more preferably a saturated aliphatic hydrocarbon having 7 to 10 carbon atoms A hydrocarbon, an aromatic hydrocarbon or a halogenated hydrocarbon may be used. Specific examples thereof include a mixture of at least one selected from heptane, octane, nonane, decane, toluene, xylene, chlorohexane and chloroheptane.

Also, the use ratio of the organic solvent to the diethoxy magnesium is preferably 1: 5 to 1:50, more preferably 1: 7 to 1:20 by weight of diethoxy magnesium in terms of organic solvent volume, If the ratio is less than 1: 5, the viscosity of the slurry increases sharply and it is difficult to uniformly stir. When the ratio is more than 1:50, the bulk density of the carrier to be produced sharply decreases or the surface of the particles becomes rough.

The titanium halide used in the preparation of the solid catalyst can be represented by the following general formula (I)

Ti (OR) _n X _(4-n) ... ... ... ... (I)

Wherein R is an alkyl group having 1 to 10 carbon atoms, X is a halogen element, and n is an integer of 0 to 3 for matching the valency of the general formula. Ti (OCH3) 2Cl2, Ti (OC2H5) 2Cl2, Ti (OC3H7) Cl3, Ti (OCH3) TiCl 4, TiCl 4, TiCl 4, TiCl 4, TiCl 4, TiCl 4, TiCl 2, Is used. These tetravalent titanium halide compounds may be used singly or in combination of two or more. The reaction temperature in step (1) is -10 to 60 ° C.

Among the two internal electron donors represented by the above step (2), the first internal electron donor is a compound represented by the following general formula (II).

………… (Ⅱ)

... ... ... ... (II)

That is, B is a compound having a monoester structure composed of aliphatic saturated hydrocarbons and cyclic saturated hydrocarbons having 1 to 20 carbon atoms, or B is a compound having a carbamate structure composed of an amino group or a linear or cyclic amino group . Each of R ₁ , R ₂ , R ₃ , R ₄ and R ₅ independently represents a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a vinyl group, a straight chain alkenyl group having 3 to 12 carbon atoms, A straight chain halogenated alkyl group having 1 to 12 carbon atoms, a branched halogenated alkyl group having 3 to 12 carbon atoms, a straight chain halogenated alkenyl group having 3 to 12 carbon atoms or a branched halogenated alkenyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, A halogen-substituted cycloalkyl group having 3 to 12 carbon atoms, a halogen-substituted cycloalkenyl group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms, more preferably a group having 1 to 12 carbon atoms A branched alkyl group having 3 to 12 carbon atoms, a vinyl group, a straight chain alkenyl group or a branched alkenyl group having 3 to 12 carbon atoms, a straight chain halogenated alkyl group having 1 to 12 carbon atoms, a branched halogenated alkyl group having 3 to 12 carbon atoms, 3 to 12 cycloalkyl groups , A cycloalkenyl group having 3 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms. Particularly preferred groups are straight chain alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, and cyclic hydrocarbons having 6 to 12 carbon atoms .

Specific examples thereof include 2-methoxyethyl acetate, 2-methoxyethylpropionate, 2-methoxyethylbutylate, 2-methoxyethylisobutylate, 2-methoxyethylpivalate, 2- Methoxyethyl 3-methylbutanoate, 2-methoxyethyl 3-methylbutanoate, 2-methoxyethyl 3,3-dimethylbutanoate, 2-methoxyethyl 2-methoxyethyl 2,2,3,3-tetramethylbutanoate, 2-methoxyethyl 3-ethyl butanoate, 2-methoxyethyl 2, 3-diethyl butanoate, 2-methoxyethyl 3,3-diethyl butanoate, 2-methoxyethyl 2,3,3-triethyl butanoate, 2-methoxyethyl 2,2,3 Methoxyethyl 2-ethyl-3-methylbutanoate, 2-methoxyethyl 3-ethyl-3-methylbutanoate, 2-methoxyethyl 2-ethyl -3,3-dimethyl butanoate, 2-methoxyethyl 2,2,3,3-tetramethylbutanoate Methoxyethyl 3-methylpentanoate, 2-methoxyethyl 2-methylpentanoate, 2-methoxyethyl 3-methylpentanoate, 2-methoxyethyl 4-methylpentanoate, 2-methoxyethyl 2,3- 2-methoxyethyl 2,2-dimethyl pentanoate, 2-methoxy ethyl 3,3-dimethyl pentanoate, 2-methoxy ethyl 4,4-dimethyl pentanoate, 2-methoxy ethyl 2-methoxyethyl 3,4-dimethylpentanoate, 2-methoxyethyl 3,3,4-trimethylpentanoate, 2-methoxyethyl 2,3,3- Trimethylpentanoate, 2-methoxyethyl 2,2,3-trimethylpentanoate, 2-methoxyethyl 2,3,4-trimethylpentanoate, 2-methoxyethyl 2,3,3-trimethylpenta 2-methoxyethyl 2,2,3,3-tetramethylphenanoate, 2-methoxyethyl 3-ethylpentanoate, 2-methoxyethyl 2,3-diethylpentanoate, 2-methoxyethyl 3,3-diethylpentanoate, 2-methoxyethyl 2,3,3-triethylpentanoate 2-methoxyethyl 2,2,3,3-tetraethylpentanoate, 2-methoxyethyl 2-ethyl-3-methylpentanoate, 2-methoxyethyl 3-ethyl- Pentanoate, 2-methoxyethyl 2-ethyl-3,3-dimethylpentanoate, 2-methoxyethyl 2,2,3,3-tetramethylpentanoate,

2-methoxyethyl cyclohexanecarboxylate, 2-methoxyethyl cyclohexanecarboxylate, 2-methoxyethyl 2-methylcyclohexanecarboxylate, 2-methoxyethyl 3-methylcyclohexanecarboxylate, 2- Carboxylate, 2-methoxyethylcyclohexyl-2-ene carboxylate, 2-methoxyethylcarbamate, 2-methoxyethylmethylcarbamate, 2-methoxyethylethylcarbamate, 2-methoxyethyl 2-methoxyethylpiperidine-1-carboxylate, 2-methoxyethyl 2-methylpiperidine-1-carboxylate, 2-methoxyethylpiperidine-1-carboxylate, 2-methoxyethyl 2,3-dimethylpiperidine-1-carboxylate, 2-methoxyethyl 2,4-dimethylpiperidine-1-carboxylate, -Carboxylate, 2-methoxyethyl 2,5-dimethylpiperidine-1-carboxylate, 2-methoxyethyl 2,6-dimethylpiperidine-1-carboxylate, 2-ethoxyethyl acetate, 2-ethoxyethyl isobutyrate, 2-ethoxyethyl pivalate, 2-ethoxy ethyl pentanoate, 2-ethoxy ethyl 3- Methylbutanoate, 2-ethoxyethyl 2,3-dimethyl butanoate, 2-ethoxyethyl 3,3-dimethyl butanoate, 2-ethoxyethyl 2,3,3-trimethyl butanoate, 2 Ethoxyethyl 2,2,3,3-tetramethylbutanoate, 2-ethoxyethyl 3-ethyl butanoate, 2-ethoxyethyl 2,3-diethyl butanoate, 2-methoxy Ethyl 3,3-diethyl butanoate, 2-ethoxyethyl 2,3,3-triethyl butanoate, 2-ethoxyethyl 2,2,3,3-tetraethyl butanoate, 2- 3-methylbutanoate, 2-ethoxyethyl 3-ethyl-3-methylbutanoate, 2-ethoxyethyl 2-ethyl-3,3-dimethylbutanoate, 2- Ethoxyethyl 2,2,3,3-tetramethyl butanoate, 2-ethoxyethyl 2-methyl pentanoate, 2-ethoxyethyl 3-methylpentanoate, 2-ethoxyethyl 4-methylpentanoate, 2-ethoxyethyl 2,3-dimethylpentanoate, 2-ethoxyethyl 2,2- Ethoxyethyl 3,3-dimethylpentanoate, 2-ethoxyethyl 4,4-dimethylpentanoate, 2-ethoxyethyl 2,4-dimethylpentanoate, 2-ethoxyethyl 3 , 4-dimethylpentanoate, 2-ethoxyethyl 3,3,4-trimethylpentanoate, 2-ethoxyethyl 2,3,3-trimethylpentanoate, 2-ethoxyethyl 2,2,3 -Trimethylpentanoate, 2-ethoxyethyl 2,3,4-trimethylpentanoate, 2-ethoxyethyl 2,3,3-trimethylpentanoate, 2-ethoxyethyl 2,2,3,3 , Tetramethylphenanoate, 2-ethoxyethyl 3-ethylpentanoate, 2-ethoxyethyl 2,3-diethylpentanoate, 2-ethoxyethyl 3,3-diethylpentanoate, 2-ethoxyethyl 2,3,3-triethylpentanoate, 2-ethoxyethyl 2,2,3,3-tetraethylpentanoate 3-methylpentanoate, 2-ethoxyethyl 2-ethyl-3-methylpentanoate, 2-ethoxyethyl 3-ethyl- 2-ethoxyethyl 2,2,3,3-tetramethylpentanoate, 2-ethoxyethylcyclohexanecarboxylate, 2-ethoxyethyl 2-methylcyclohexanecarboxylate, 2- Ethoxyethylcyclohexanecarboxylate, 2-ethoxyethylcyclohex-2-enecarboxylate, 2-ethoxyethylcarbamate, 2-ethoxyethylcyclohexanecarboxylate, 2- -Ethoxyethyl methyl carbamate, 2-ethoxyethyl ethyl carbamate, 2-ethoxy ethyl dimethyl carbamate, 2-ethoxy ethyl diethyl carbamate, 2-ethoxy ethyl piperidine- , 2-ethoxyethyl 2-ethylpiperidine-1-carboxylate, 2-ethoxyethyl 3-ethylpiperidine-1-carboxylate, 2-ethoxyethyl 2,3-dimethylpiperidine -1-carboxylate, 2- Ethoxyethyl 2,4-dimethylpiperidine-1-carboxylate, 2-ethoxyethyl 2,5-dimethylpiperidine-1-carboxylate, 2-ethoxyethyl 2,6- Di-1-carboxylate, and the like.

The second internal electron donor is not particularly limited and can be used without limitation as long as it is a compound that can be used as an internal electron donor in the production of a Ziegler-based catalyst for olefin polymerization such as alcohols, ethers, ketones, and carboxylic acids. Among them, it is preferable to use a carboxylic acid compound, and it is more preferable to use a mixture of one or more selected from benzene-1,2-dicarboxylic ester compounds as a second internal electron donor. Specific examples of the benzene-1,2-dicarboxylic acid ester compound include dimethyl phthalate, diethyl phthalate, dinompropyl phthalate, diisopropyl phthalate, dinomal butyl phthalate, diisobutyl phthalate dinomentyl phthalate, di (2-methylbutyl) phthalate, di (3-methylbutyl) phthalate, di (3-methylpentyl) citalate, diisobutylphthalate, dineohexylphthalate, di (2-methylpentyl) phthalate, diisobutyl phthalate, dineoheptyl phthalate, dinohexyl phthalate, dibutyl phthalate, dibutyl phthalate, dibutyl phthalate, (2-methylheptyl) phthalate, diisooctyl phthalate, di (3-ethylhexyl) phthalate, dineoctyl phthalate, dinononyl phthalate, diisobutyl phthalate, di Carbonyl phthalate, and the like Dino end decyl phthalate, diisodecyl phthalate.

In the step (2), the temperature of the resultant product of step (1) is gradually raised to 60 to 150 ° C, preferably 80 to 130 ° C, and the internal electron donor is added during the temperature raising process to perform the reaction for 1 to 3 hours If the temperature is less than 60 ° C or the reaction time is less than 1 hour, the reaction is difficult to be completed. If the temperature exceeds 150 ° C or the reaction time exceeds 3 hours, the polymerization reaction of the resultant catalyst Or the stereoregularity of the polymer may be lowered.

As long as the first and second inner electron donors are charged during the temperature raising process, the charging temperature and the number of times of charging are not limited to a great extent, and two inner electron donors may be injected simultaneously or at different temperatures. Although the total amount of the two internal electron donors is not limited, the total internal electron donor is preferably 2.5 to 30 wt%, and the total number of moles of the internal electron donor used is preferably 1 mol to 1 mol of the dialkoxymagnesium used, The second internal electron donor is preferably used in an amount of 0.001 to 2.0 moles, and the second internal electron donor is preferably used in an amount of 0.001 to 2.0 moles. If it is outside the above range, the polymerization activity of the resultant catalyst or the stereoregularity of the polymer may be lowered.

The step (3) of the production of the solid catalyst is a step of reacting the result of step (2) with the titanium halide at a temperature of 60 to 150 ° C, preferably 80 to 130 ° C. An example of the titanium halide to be used at this time is titanium halide of the above-mentioned general formula (I).

In the production process of the solid catalyst, the reaction in each step is preferably carried out in a reactor equipped with a stirrer in which water and the like are sufficiently removed in a nitrogen gas atmosphere.

The solid catalyst of the present invention produced by the above process comprises magnesium, titanium, halogen and an internal electron donor. Considering the catalytic activity, the solid catalyst comprises 5 to 40 wt% of magnesium, 0.5 to 10 wt% of titanium , 50 to 85% by weight of halogen, 0.1 to 20% by weight of the first inner electron donor and 0.1 to 20% by weight of the second inner electron donor.

The solid catalyst prepared by the catalyst preparation method of the present invention can be suitably used for the propylene polymerization or copolymerization method, and the propylene polymerization or copolymerization method using the solid catalyst produced by the present invention is characterized in that the solid catalyst, the cocatalyst, Polymerizing propylene in the presence of a donor or copolymerizing propylene with other alpha olefins.

The solid catalyst can be used in the prepolymerized state with ethylene or alpha olefin before being used as a component of the polymerization reaction.

The prepolymerization reaction can be carried out in the presence of a hydrocarbon solvent (e.g. hexane), the catalyst component and an organoaluminum compound (e.g. triethylaluminum) at sufficiently low temperatures and under ethylene or alpha olefin pressure conditions. Pre-polymerization helps encapsulate the catalyst particles in the polymer to maintain the shape of the catalyst to improve the shape of the polymer after polymerization. The weight ratio of polymer / catalyst after pre-polymerization is preferably about 0.1 to 20: 1. As the promoter component in the propylene polymerization or copolymerization method, an organometallic compound of Group II or Group III of the periodic table can be used, and as an example thereof, an alkyl aluminum compound is preferably used. The alkyl aluminum compound is represented by the general formula ( III ).

AlR ₃ (III)

Here, R is an alkyl group having 1 to 6 carbon atoms.

Specific examples of the alkylaluminum compound include trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, triisobutylaluminum and trioctylaluminum.

The ratio of the cocatalyst component to the solid catalyst component varies depending on the polymerization method, but it is preferable that the molar ratio of metal atoms in the cocatalyst component to the titanium atom in the solid catalyst component is in the range of 1 to 1000, And more preferably in the range of 10 to 300. If the molar ratio of the metal atom in the cocatalyst component to the titanium atom in the solid catalyst component, for example, the aluminum atom, is out of the above range of 1 to 1000, the polymerization activity is greatly reduced.

In the propylene polymerization or copolymerization method, at least one of the alkoxysilane compounds represented by the following formula ( IV ) may be used as the external electron donor:

R ¹ _m R ² _n Si (OR ³ ) _(4-mn) (IV)

Wherein R ¹ and R ² may be the same or different and are a linear or branched or cyclic alkyl group or an aryl group having 1 to 12 carbon atoms, R ³ is a linear or branched alkyl group having 1 to 6 carbon atoms, and m , n is 0 or 1, respectively, and m + n is 1 or 2.

Specific examples of the external electron donor include, but are not limited to, n-propyltrimethoxysilane, dinormalpropyldimethoxysilane, isopropyltrimethoxysilane, diisopropyldimethoxysilane, n-butylbutyltrimethoxysilane, dinormal butyldimethoxy Silane, isobutyltrimethoxysilane, diisobutyldimethoxysilane, tertiarybutyltrimethoxysilane, ditertiarybutyldimethoxysilane, n-pentyltrimethoxysilane, dinormalpentyldimethoxysilane, cyclopentyltrimethoxy Silane, dicyclopentyldimethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylethyldimethoxysilane, cyclopentylpropyldimethoxysilane, cyclohexyltrimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldimethoxysilane, , Cyclohexyl ethyl dimethoxy silane, cyclohexylpropyl dimethoxy silane, cycloheptyl trimethoxy silane, dicycloheptyl dimethoxy silane, cycloheptyl methyl dimethoxy silane , Cycloheptylethyldimethoxysilane, cycloheptyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, phenylethyldimethoxysilane, phenylpropyldimethoxysilane, n-propyltriethoxy Silane, dinormalpropyldiethoxysilane, isopropyltriethoxysilane, diisopropyldiethoxysilane, n-butylbutyltriethoxysilane, dinormalbutyldiethoxysilane, isobutyltriethoxysilane, diisobutyldiethoxysilane, Tricyclohexyldiethoxysilane, cyclopentyldiethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylmethyldiethoxysilane, Cyclopentylethyldiethoxysilane, cyclopentylpropyldiethoxysilane, cyclohexyltriethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylmethyldiethoxysilane, Cyclohexylpropyldiethoxysilane, cyclohexylpropyldiethoxysilane, cyclohexylethyldiethoxysilane, cyclohexylpropyldiethoxysilane, cyclohexylpropyldiethoxysilane, cyclohexylpropyldiethoxysilane, cyclohexylpropyldiethoxysilane, cyclohexylpropyldiethoxysilane, cyclohexylpropyldiethoxysilane, cycloheptyltriethoxysilane, Triethoxysilane, diphenyldiethoxysilane, phenylmethyldiethoxysilane, phenylethyldiethoxysilane, and phenylpropyldiethoxysilane. Of these, at least one of them may be used alone or in combination.

Although the amount of the external electron donor to be used for the solid catalyst varies depending on the polymerization method, the molar ratio of the silicon atoms in the external electron donor to the titanium atom in the catalyst component is preferably in the range of 0.1 to 500, more preferably 1 to 100 Is more preferable. If the molar ratio of the silicon atom in the external electron donor to the titanium atom in the solid catalyst component is less than 0.1, the resulting stereoregularity of the resulting propylene polymer becomes significantly low, and if it exceeds 500, the polymerization activity of the catalyst is significantly reduced .

In the above-mentioned propylene polymerization or copolymerization method, the polymerization reaction temperature is preferably 20 to 120 ° C. If the polymerization reaction temperature is less than 20 ° C, the reaction does not proceed sufficiently, which is undesirable. It is undesirable because it causes considerable deterioration and adversely affects the physical properties of the polymer.

The present invention relates to a process for producing a solid catalyst for the production of polypropylene, which comprises a solid catalyst prepared by reacting a dialkoxy magnesium with a metal halide, a titanium halide, an organic electron donor and the like, and a process for producing a polypropylene It is possible to use an internal electron donor containing a carbonyl group and an alkoxy group among the two types of organic electron donors used in the present invention to form various forms such as a slurry polymerization method, a bulk polymerization method and a gas phase polymerization method It is possible to produce a polypropylene which is applicable to the polymerization process of propylene and which has high activity and stereoregularity.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

Example  One

1. Preparation of solid catalyst

To a glass reactor equipped with a stirrer having a volume of 1 liter sufficiently substituted with nitrogen, 112 ml of toluene and 15 g of diethoxy magnesium (sphere having an average particle size of 20 μm and a particle size distribution index of 0.86 and an apparent density of 0.35 g / cc) , 20 ml of titanium tetrachloride was diluted in 30 ml of toluene and added over 1 hour. While the temperature of the reactor was raised to 100 ° C, 3.8 g of diisobutylphthalate and 1.5 g of 2-ethoxyethylbutylate The mixture was injected. The mixture was maintained at 100 DEG C for 2 hours, then cooled down to 90 DEG C, stirring was stopped, the supernatant was removed, and further washed once with 200 mL of toluene. 120 ml of toluene and 20 ml of titanium tetrachloride were added thereto, and the temperature was raised to 100 ° C and maintained for 2 hours. This procedure was repeated once. The aged slurry mixture thus obtained was washed twice with 200 ml of toluene per one time and washed with n-hexane at 40 ° C for five times with 200 ml each time to obtain a pale yellow solid catalyst component. The titanium content in the solid catalyst component obtained by flowing in flowing nitrogen for 18 hours was 2.1% by weight.

2. Polymerization of polypropylene

10 mg of the above solid catalyst, 10 mmol of triethylaluminum and 1 mmol of dicyclopentylmethyldimethoxysilane were fed into a 4-liter high-pressure stainless steel reactor. Then, 7000 ml of hydrogen and 2.4 L of liquid propylene were added in turn, and the temperature was raised to 70 ° C to perform polymerization. After 2 hours from the start of the polymerization, the temperature of the reactor was dropped to room temperature, and the valve was opened to completely degas propylene inside the reactor.

The resulting polymer was analyzed and is shown in Table 1.

Here, the catalytic activity and stereoregularity were determined by the following method.

① Catalyst activity (kg-PP / g-cat) = amount of polymer produced (kg) ÷ amount of catalyst (g)

(2) Stereoregularity (XI): Weight% of insoluble matter crystallized and crystallized in mixed xylene

(3) Melt flowability (g / 10 min): Measured by ASTM 1238 at 230 ° C under a load of 2.16 kg

Example  2

In the preparation of the solid catalyst of Example 1, 3.0 g of diisobutyl phthalate was poured instead of the mixture of diisobutyl phthalate and 2-ethoxyethyl butyrate, and the mixture was heated to 40 to 60 ° C to obtain 2-methoxyethyl 2.5 g of pivalate was injected to prepare a catalyst. The content of titanium in the solid catalyst component was 2.0% by weight. Next, polypropylene polymerization was carried out in the same manner as in Example 1, and the results are shown in Table 1.

Example  3

Example 1 1. Preparation of the solid catalyst A mixture of 4.2 g of diisobutylphthalate and 0.8 g of 2-methoxyethylcyclohexanecarboxylate in place of the mixture of diisobutylphthalate and 2-ethoxyethylbutylate To prepare a catalyst. The content of titanium in the solid catalyst component was 2.1% by weight. Next, polypropylene polymerization was carried out in the same manner as in Example 1, and the results are shown in Table 1.

Example  4

In the preparation of the solid catalyst of Example 2, 3.5 g of diisobutyl phthalate and 2.1 g of 2-ethoxyethyl propionate were charged in place of diisobutyl phthalate and 2-methoxyethyl pivalate to prepare a catalyst. The content of titanium in the solid catalyst component was 2.0% by weight. Next, polypropylene polymerization was carried out in the same manner as in Example 1, and the results are shown in Table 1.

Example  5

1. Preparation of solid catalyst

Into a glass reactor equipped with a stirrer having a volume of 1 liter sufficiently substituted with nitrogen, 112 ml of toluene and 15 g of diethoxy magnesium (spherical having an average particle diameter of 20 탆, a particle size distribution index of 0.86 and an apparent density of 0.35 g / cc) 20 ml of titanium tetrachloride was diluted with 30 ml of toluene while being kept at 10 ° C and added over 1 hour. Then, 3.0 g of diisobutyl phthalate was added while raising the temperature of the reactor to 100 ° C. The mixture was maintained at 100 DEG C for 2 hours, then cooled down to 90 DEG C, stirring was stopped, the supernatant was removed, and further washed once with 200 mL of toluene. To this was added 120 ml of toluene and 20 ml of titanium tetrachloride, and then 3.0 g of 2-ethoxyethyl isobutyrate was poured therein. Then, the temperature was raised to 100 ° C and maintained for 2 hours. This procedure was repeated once. The aged slurry mixture thus obtained was washed twice with 200 ml of toluene per one time and washed with n-hexane at 40 ° C for five times with 200 ml each time to obtain a pale yellow solid catalyst component. The titanium content in the solid catalyst component obtained by flowing in flowing nitrogen for 18 hours was 2.1% by weight.

Example  6

In the preparation of the solid catalyst of Example 6, instead of diisobutyl phthalate and 2-ethoxyethyl isobutyrate, 4.8 g of diisobutyl phthalate and 1.1 g of 2-methoxyethylpentanoate were introduced respectively to prepare a catalyst Respectively. The titanium content in the solid catalyst component was 2.3% by weight. Next, polypropylene polymerization was carried out in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example  One

Example 1, 1. In the preparation of the solid catalyst, a catalyst was prepared using 4.7 g of diisobutyl phthalate instead of a mixture of diisobutyl phthalate and 2-ethoxyethyl butyrate. The titanium content in the solid catalyst component was 2.2% by weight. Next, polypropylene polymerization was carried out in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example  2

1. Preparation of solid catalyst

150 ml of toluene, 12 ml of tetrahydrofuran, 20 ml of butanol and 21 g of magnesium chloride were added to a glass reactor equipped with a stirrer having a volume of 1 liter sufficiently substituted with nitrogen, and the temperature was raised to 110 ° C and maintained for 1 hour to obtain a homogeneous solution. The temperature of the solution was cooled to 15 ° C and 25 ml of titanium tetrachloride was added. The temperature of the reactor was elevated at 60 ° C over 1 hour, aged for 10 minutes, allowed to stand for 15 minutes to allow the carrier to settle, Respectively. The remaining slurry in the reactor was charged with 200 ml of toluene and washed by repeating stirring, setting, and removal of the supernatant twice.

After 150 ml of toluene was poured into the slurry thus obtained, 25 ml of titanium tetrachloride was diluted with 50 ml of toluene at 15 ° C and added over 1 hour. The temperature of the reactor was increased to 30 ° C at a rate of 0.5 ° C per minute. The reaction mixture was maintained at 30 DEG C for 1 hour, then 7.5 mL of diisobutylphthalate was introduced, and the temperature was further raised to 110 DEG C at a rate of 0.5 DEG C per minute.

After maintaining at 110 DEG C for 1 hour, the temperature was lowered to 90 DEG C and stirring was stopped, and the supernatant was removed, and further washed once with 200 mL of toluene in the same manner. 150 ml of toluene and 50 ml of titanium tetrachloride were added thereto, and the temperature was elevated to 110 ° C and maintained for 1 hour. The aged slurry mixture was washed twice with 200 ml of toluene and washed with hexane (200 ml) at 40 캜 for 5 times each time to obtain a pale yellow solid catalyst component. The titanium content in the solid catalyst component obtained by drying in flowing nitrogen for 18 hours was 3.3% by weight.

activation
(g-PP / g cat 2h) X / S
(wt%) MI
(g / 10 min) MWD Example 1 91,000 0.6 23 4.3 Example 2 89,000 0.5 25 4.2 Example 3 86,000 0.6 30 4.1 Example 4 83,000 0.5 27 4.3 Example 5 90,000 0.4 22 4.3 Example 6 87,500 0.6 20 4.2 Comparative Example 1 83,000 1.5 27 4.1 Comparative Example 2 66,000 1.9 28 4.1

Claims (5)

Titanium, magnesium, halogen and an internal electron donor represented by the following general formula (II): < EMI ID =

... ... ... ... (II)
Each of R ₁ , R ₂ , R ₃ , R ₄ and R ₅ independently represents a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a vinyl group, a straight chain alkenyl group having 3 to 12 carbon atoms, A straight chain halogenated alkyl group having 1 to 12 carbon atoms, a branched halogenated alkyl group having 3 to 12 carbon atoms, a straight chain halogenated alkenyl group having 3 to 12 carbon atoms or a branched halogenated alkenyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, A halogen-substituted cycloalkyl group having 3 to 12 carbon atoms, a halogen-substituted cycloalkenyl group having 3 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, and a cyclic hydrocarbon group having 6 to 12 carbon atoms ,
B is a compound having a monoester structure composed of aliphatic saturated hydrocarbons and cyclic saturated hydrocarbons having 1 to 20 carbon atoms, or B is a compound having a carbamate structure composed of an amino group or a linear or cyclic amino group. The process according to claim 1, wherein the solid catalyst comprises 5 to 40 wt% of magnesium, 0.5 to 10 wt% of titanium, 50 to 85 wt% of halogen, and 2.5 to 30 wt% of total internal electron donor Solid catalyst. The solid catalyst for polymerization of propylene according to claim 1, wherein the solid catalyst comprises 0.01 to 20 wt% of an alkoxyester internal electron donor. The solid catalyst for polymerization of propylene according to claim 1, wherein the two internal electron donors used in the solid catalyst include alkoxy esters and phthalic acid esters. A process for producing a solid catalyst according to any one of claims 1 to ₃ , which comprises reacting AlR ₃ (wherein R is an alkyl group having 1 to 6 carbon atoms) as a cocatalyst and R ¹ _m R ² _n Si (OR ³ ) _{(4 -mn} wherein R ¹ and R ² may be the same or different and each is a linear or branched or cyclic alkyl group having 1 to 12 carbon atoms or an aryl group and R ³ is a linear or branched An alkyl group, m and n are each 0 or 1, and m + n is 1 or 2, or copolymerizing propylene with other alpha olefins.