KR100870818B1 - Olefin polymerization or copolymerization method - Google Patents

Abstract

The present invention relates to an olefin polymerization or copolymerization method, comprising: (a) a solid complex titanium catalyst prepared by the production process comprising the following steps: (1) mixing a magnesium halide compound with a cyclic ether and at least one alcohol compound Dissolving in an oxygen-containing solvent as a solvent to obtain a magnesium compound solution, (2) first reacting the magnesium compound solution with a titanium halide compound at -10 to 30 ° C, and then raising or aging to obtain particles. Reacting with a titanium halide compound to prepare a carrier; (3) reacting the carrier with a phthalic acid dialkyl ester electron donor having a titanium halide compound and an alkyl group having 9 to 13 carbon atoms to prepare a supported titanium catalyst. (4) washing the prepared catalyst with a hydrocarbon solvent at a temperature of 40-200 ° C .; (b) organometallic compounds of Groups II or III of the Periodic Table; And (c) an organosilicon compound having the general formula of (C ₆ H ₁₁ ) ₂ Si (OR) ₂ , wherein R represents an alkyl group having 1 to 5 carbon atoms. do. The polymer produced by the olefin polymerization or copolymerization method of the present invention has a wide molecular weight distribution by using a catalyst having excellent catalytic activity and hydrogen reactivity and having high stereoregularity, thereby increasing productivity of the polymerization process. .

 Olefin polymerization, cyclic ethers, oxygen-containing solvents, titanium halide compounds, solid titanium catalysts, phthalic acid dialkyl esters

Description

Olefin polymerization or copolymerization method {OLEFIN POLYMERIZATION OR COPOLYMERIZATION METHOD}

The present invention relates to an olefin polymerization or copolymerization method, and more particularly, by controlling the catalyst particle size and shape in an easier manner, by using a catalyst having excellent catalytic activity and hydrogen reactivity and having high stereoregularity, The present invention relates to an olefin polymerization or copolymerization method having a wide molecular weight distribution.

Although many olefin polymerization catalysts and polymerization methods using the same have been reported so far, efforts to improve productivity or product quality by improving physical properties of a polymer obtained using the catalyst invented in order to give the catalyst a greater commercial meaning. There is a continuing need to improve the activity and stereoregularity of the catalyst itself.

A number of olefin polymerization catalysts and catalysts containing magnesium have been reported, and in particular, many methods for preparing a catalyst using a solution of a magnesium compound to control the particle shape and size of the catalyst and the like are known.

There is a method of obtaining a magnesium solution by reacting a magnesium compound with an electron donor such as an alcohol, an amine, an ether, an ester, a carboxylic acid, or the like in the presence of a hydrocarbon solvent. Reference is made to published patent publication no. 58-83006. In addition, U.S. Patent Nos. 4,315,874, 4,399,054, and 4,071,674 report a method for preparing magnesium solutions.

Tetrahydrofuran, a cyclic ether, is variously used as a magnesium chloride compound (for example, US Pat. No. 4,482,687), as an additive for a promoter (US Pat. No. 4,158,642), and as a solvent (US Pat. No. 4,477,639). Has been.

U.S. Patent Nos. 4,347,158, 4,422,957, 4,425,257, 4,618,661, and 4,680,381 propose a method of preparing a catalyst after pulverizing a Lewis acid compound such as aluminum chloride to magnesium chloride as a support.

However, in the above patents, the catalytic activity is complemented, but there are irregularities in the shape of the catalyst such as the shape, size, and size distribution of the catalyst, and there are disadvantages in that stereoregularity must be complemented.

As described above, the improvement aspect for improving the commercial value of the catalyst for alpha olefin polymerization is to produce a catalyst having high polymerization activity and stereoregularity and to improve the quality of the product, and to control the shape and size of the catalyst to improve productivity. Efforts have been made to increase the production cost and to improve the production yield and activity of the catalyst in the production of the catalyst, and efforts are being made to reduce the production cost.

The present invention has been made to overcome the above problems, an object of the present invention by using a catalyst having excellent catalytic activity and hydrogen reactivity, high stereoregularity, olefin polymerization or copolymerization method having a wide molecular weight distribution To provide.

The olefin polymerization or copolymerization method of the present invention,

(a) a solid titanium catalyst prepared by the production process comprising the following steps:

(1) dissolving a magnesium halide compound in an oxygen solvent which is a mixed solvent of a cyclic ether and at least one alcohol compound to obtain a magnesium compound solution,

(2) preparing a carrier by first reacting the magnesium compound solution with a titanium halide compound at -10 to 30 ° C., then raising the temperature or aging to obtain particles, and then secondly reacting with the titanium halide compound to prepare a carrier,

(3) reacting the carrier with a titanium halide compound and an electron donor to prepare a titanium supported catalyst, and

(4) washing the prepared catalyst with a hydrocarbon solvent at a temperature of 40 ~ 200 ℃;

(b) organometallic compounds of Groups II or III of the Periodic Table; And

(c) (C ₆ H ₁₁ ) ₂ Si (OR) ₂ (wherein R represents an alkyl group having 1 to 5 carbon atoms), characterized in that it is carried out in the presence of an external electron donor, an organosilicon compound having a general formula. .

Examples of the magnesium halide compound used in step (1) of the method for preparing (a) solid titanium catalyst include magnesium halide, alkyl magnesium halide, alkoxymagnesium halide, and aryloxymagnesium halide. The magnesium halide compound may be used as a mixture of two or more kinds, and is effective even when used in the form of a complex with another metal.

The cyclic ether used in the step (1) is preferably a cyclic ether having 3 to 6 carbon atoms and a derivative thereof, more preferably tetrahydrofuran, 2-methyl tetrahydrofuran, and most preferably Preferably tetrahydrofuran.

The alcohol compound used in the step (1) is preferably a monovalent or polyhydric alcohol having 1 to 20 carbon atoms, more preferably an alcohol containing 2 to 12 carbon atoms.

The amount of the oxygen-containing solvent used in the step (1) is 1 to 15 mol, preferably about 2 to 10 mol, per mol of the magnesium atom of the magnesium halide compound. When the amount of use is less than 1 mole, dissolution of the magnesium halide compound is difficult, and when it exceeds 15 moles, the amount of the magnesium halide compound to be added to obtain the catalyst particles is too large, and the particle is also difficult to control.

Since the use ratio of the cyclic ether and the alcohol, which are the oxygen-containing solvent used in the step (1), depends on the particle characteristics and the size of the catalyst prepared according to the use ratio, it can be used by appropriately adjusting, preferably the cyclic 0.5 to 3.5 moles of alcohol per mole of ether.

The dissolution temperature in step (1) depends on the type and amount of cyclic ether and alcohol, but is preferably 20 to 200 ° C, more preferably about 50 to 150 ° C.

In step (1), a hydrocarbon solvent may be additionally used as a diluent. Examples of the hydrocarbon solvent include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane and kerosene; Alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; Aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; Examples include halogenated hydrocarbons such as trichloroethylene, carbon tetrachloride and chlorobenzene.

Step (2) of the method for preparing a solid titanium catalyst includes the titanium halide compound represented by the following general formula (I) in the magnesium compound solution obtained in step (1) so that particles do not form at -10 to 30 ° C. Oxygen solvent: The titanium halide compound is first introduced to a molar ratio of 1: 3.0 to 10, and the particles are precipitated by raising or aging the temperature, and then the titanium halide compound represented by the following general formula (I) Oxygen solvent: The titanium halide compound is charged into the secondary so that the molar ratio of 1: 0.3 to 7.0 is reacted to obtain solid particles used as a carrier.

Ti (OR) _a X _(4-a) ‥‥‥ (I)

[Where R represents an alkyl group having 1 to 10 carbon atoms, X is a halogen group element, and a is an integer of 0 to 3 to match the valence of the general formula.]

When the titanium halide compound is first added to the magnesium compound solution in the step (2), it is necessary to adjust the conditions such as the input temperature, the molar ratio of the oxygenated solvent and the titanium halide compound to prevent precipitation during the first charge. It is important to control the shape, and the production rate of the catalyst can be increased by adding a titanium halide compound and reacting it after the formation of carrier particles.

Step (3) in the method for preparing a solid titanium catalyst (a) includes a phthalic acid dialkyl ester having a titanium halide compound and an alkyl group having 9 to 13 carbon atoms and an alkyl group having 1 to 8 carbon atoms. Reaction with the carboxylic acid alkyl ester mixed electron donor to support titanium, which may be completed in one reaction, but is preferably carried out in two or three or more reactions.

Preferably, in step (3), the carrier obtained in step (2) is reacted with the titanium halide compound or with an appropriate electron donor, and the remaining slurry after separating the liquid mixture is subjected to the titanium compound and the electron donor After reacting with once again, the solid component is separated and dried to obtain a catalyst.

Examples of the phthalic acid dialkyl ester having an alkyl group having 9 to 13 carbon atoms used in step (3) include dialkyl phthalates such as diisononyl phthalate, diisodecyl phthalate, and tertiary decyl phthalate and derivatives thereof. Can be mentioned.

The amount of the phthalic acid dialkyl ester electron donor used in the step (3) is preferably a molar ratio of 1: 0.08 to 2.5 of the magnesium halide compound: phthalic acid dialkyl ester of the step (1).

Step (4) of the method for preparing a solid titanium catalyst (a) is a step of washing the catalyst prepared in step (3) with a hydrocarbon solvent at a high temperature, through which a high stereoregular catalyst is completed.

Examples of hydrocarbon solvents used in step (4) include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane and kerosene, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, benzene, toluene, xylene and ethylbenzene; And aromatic hydrocarbons such as trichloroethylene, carbon tetrachloride and chlorobenzene.

In order to further enhance the stereoregularity of the solid complex titanium catalyst, the temperature at the time of washing in the step (4) is 40 to 200 ° C, preferably 50 to 150 ° C.

The polymerization or copolymerization method of the olefin according to the present invention comprises (a) a solid titanium catalyst, (b) an organometallic compound of group II or group III of the periodic table and (c) (C ₆ H ₁₁ ) ₂ Si (OR) ₂ (wherein R represents an alkyl group having 1 to 5 carbon atoms), a process performed in the presence of an external electron donor which is an organosilicon compound having a general formula.

Examples of the organometallic compounds of (b) Group II or III of the periodic table, used as cocatalysts in the olefin polymerization or copolymerization process, include trialkylaluminum such as triethylaluminum and tributylaluminum, triisoprenylaluminum and Trialkenyl aluminum, such as partially alkoxylated alkyl aluminum, for example, dialkyl aluminum alkoxide, such as diethyl aluminum ethoxide and dibutyl aluminum butoxide, ethyl aluminum sesquiethoxide and butyl aluminum sesqui Alkylaluminum dihalides such as alkylaluminum sesquialkoxy, ethylaluminum dichloride, propylaluminum dichloride and butylaluminum dibromide, such as ethoxide, partially halogenated aluminum, diethylaluminum hydride or dibutylaluminum hydride; Such as dialkylaluminum hydride, ethylal Partially alkoxylated and halogenated alkylaluminums such as luminium ethoxychloride, butylaluminum butoxychloride and ethylaluminum ethoxybromide and the like.

The use ratio of the organometallic compound of (b) Periodic Table Group II or Group III to the solid titanium catalyst used in the present invention depends on the activity and the polymer size of the catalyst prepared according to the usage ratio, It can be used by adjusting suitably, 1.0-1500 mol is preferable per mol of titanium of a catalyst.

External electrons which are organosilicon compounds having the general formula of (c) (C ₆ H ₁₁ ) ₂ Si (OR) ₂ , wherein R represents an alkyl group having 1 to 5 carbon atoms, used in the olefin polymerization or copolymerization process. The donor is preferably dicyclohexyldimethoxysilane having a methoxy group as the alkoxy group or dicyclohexyl diethoxysilane having an ethoxy group as the alkoxy group.

The preferred amount of the (c) organosilicon compound is preferably adjusted to 0.5 to 300 moles per mole of titanium of the catalyst in consideration of catalytic activity, stereoregularity of the polymer and molecular weight distribution of the polymer.

Examples of olefin polymerization or copolymerization according to the present invention include propylene polymerization; Copolymerization between olefins such as ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene and 1-hexyl; And copolymerization of conjugated or nonconjugated dienes having a polyunsaturated compound.

The present invention may be understood in more detail by the following examples, which are intended to illustrate the present invention and are not intended to limit the protection scope of the present invention.

[ Example ]

Example  One

Preparation of Solid Titanium Catalysts

Step 1: Prepare Magnesium Compound Solution

300 g of MgCl ₂ , 4.5 kg of toluene, 350 g of tetrahydrofuran, and 600 g of butanol were added to a 10 L reactor equipped with a mechanical stirrer replaced with a nitrogen atmosphere. .

Step 2: prepare the carrier

After cooling the temperature of the solution obtained in the step 1 in 20 ℃ and turning on the TiCl ₄ 700g, and the temperature was raised over a period of 1 hour the temperature of the reactor at 60 ℃, exothermic polymerization took place and the reactor reached 60 ℃, where the TiCl ₄ 280g 40 minutes was added and reacted for 30 minutes. After the reaction, the mixture was allowed to stand for 30 minutes to settle the carrier and remove the upper solution. 2 kg of toluene was added to the slurry remaining in the reactor, and the process of stirring, standing, and removing the supernatant was repeated three times.

Step 3: prepare the catalyst

2 kg of toluene and 2.0 kg of TiCl ₄ were added to the carrier prepared in step 2 at a stirring speed of 250 rpm, and the temperature of the reactor was raised to 110 ° C. for 1 hour, aged for 1 hour, and left to stand for 15 minutes. After sinking, the supernatant was separated. To this, 2 kg of toluene, 2.0 kg of TiCl ₄ , and diisononyl phthalate were added at 0.11 mol per ₂ mol of MgCl. The temperature of the reactor is raised to 113 ° C., and the reaction is maintained for 1 hour. After the reaction, the mixture was allowed to stand for 30 minutes to separate the supernatant, and 2.0 kg of toluene and 2.0 kg of TiCl ₄ were injected again, followed by reaction at 100 ° C. for 30 minutes. After the reaction was stirred and allowed to stand for 30 minutes, the supernatant was separated.

Step 4: wash

2.0 kg of hexane was added to the catalyst slurry separated in step 3, followed by stirring while maintaining the temperature of the reactor at 40 ° C. for 30 minutes. The stirring was stopped and the supernatant was separated after standing for 30 minutes. Hexane was added to the remaining catalyst slurry layer and washed six times in the same manner to prepare a final solid titanium catalyst.

Particle size distribution of the carrier and catalyst was measured using a laser particle analyzer (Mastersizer X, Malvern Instruments), and the composition of the catalyst was analyzed by ICP.

The catalyst prepared as described above had an average particle size of about 25 μm and a titanium content of 1.7 wt%.

polymerization

Propylene polymerization was performed to evaluate the performance of the prepared catalyst. In a glove box maintained under a nitrogen atmosphere, about 7 mg of the prepared catalyst was weighed and sealed in a glass bulb, which was mounted in a 4L high pressure reactor so that the glass bulb could be broken and the reaction started at the same time of stirring, followed by nitrogen. It was purged for time so that the atmosphere of the reactor became dry nitrogen. To this, 0.7 mmol of dicyclohexyldimethoxysilane was added as a triethylaluminum (Al / Ti molar ratio = 850) and an external electron donor, and the reactor was sealed. After injection of 1,000 ml of hydrogen, 2,400 ml of liquid propylene was added using a syringe pump, and stirred to break the glass bulb to initiate the polymerization reaction, while simultaneously raising the temperature of the reactor to 70 ° C. over 20 minutes. The polymerization was carried out. After 1 hour of reaction, the unreacted propylene was vented to air, and the temperature of the reactor was lowered to room temperature. The resulting polymer was dried in a vacuum oven at 50 ° C. and then weighed. The prepared polypropylene powder was analyzed by the conventional MI (melt index) analysis and molecular weight distribution (Mw / Mn) through GPC, the results are shown in Table 1.

Example  2

In Step 3 of preparing the solid titanium catalyst of Example 1, the catalyst was prepared under the same conditions as in Example 1 except that the catalyst was prepared using diisodecylphthalate at 0.11 mol per ₂ mol of MgCl, and the analysis results are shown in Table 1 below. Indicated.

Example  3

In Step 3 of preparing the solid titanium catalyst of Example 1, the catalyst was prepared under the same conditions as in Example 1 except that the catalyst was prepared using 0.15 mol of tertiary decylphthalate per ₂ mol of MgCl, and the analysis results are shown in Table 1 below. Indicated.

Example  4

In Step 3 of preparing the solid titanium catalyst of Example 1, the catalyst was prepared under the same conditions as in Example 1, except that the catalyst was prepared using diisononylphthalate at 0.15 mol per ₂ mol of MgCl, and the analysis results are shown in Table 1 below. Indicated.

Example  5

In step 3 of preparing the solid titanium catalyst of Example 1, the catalyst was prepared under the same conditions as in Example 1 except that the catalyst was prepared using diisononylphthalate at 0.20 mol per ₂ mol of MgCl, and the analysis results are shown in Table 1 below. Indicated.

Example  6

In Step 3 of preparing the solid titanium catalyst of Example 1, the catalyst was prepared under the same conditions as in Example 1, except that the catalyst was prepared using diisodecylphthalate at 0.15 mol per ₂ mol of MgCl, and the analysis results are shown in Table 1 below. Indicated.

Example  7

In the third step of the solid titanium catalyst of Example 1, the catalyst was prepared under the same conditions as in Example 1 except that the catalyst was prepared using diisononylphthalate at 0.20 mol per ₂ mol of MgCl, and the analysis results are shown in Table 1 below. Shown in

Example  8

In step 3 of preparing the solid titanium catalyst of Example 1, diisodecylphthalate was used at 0.11 mole per ₂ moles of MgCl, and 0.35 mmol of dicyclohexyl dimethoxysilane was used as the external electron donor during polymerization with the prepared catalyst. Was carried out under the same conditions as in Example 1, and the analysis results are shown in Table 1.

Example  9

In step 3 of preparing the solid titanium catalyst of Example 1, diisodecylphthalate was used at 0.11 mol per ₂ mol of MgCl, except that 1.4 mmol of dicyclohexyl dimethoxysilane was used as the external electron donor in the polymerization with the prepared catalyst. Was carried out under the same conditions as in Example 1, and the analysis results are shown in Table 1.

Comparative example  One

In Step 3 of preparing the solid titanium catalyst of Example 1, the catalyst was prepared under the same conditions as in Example 1, except that the catalyst was prepared using diisobutylphthalate at 0.15 mole per ₂ moles of MgCl, and the analysis results are shown in Table 1 below. Indicated.

Comparative example  2

In Step 3 of preparing the solid titanium catalyst of Example 1, the catalyst was prepared under the same conditions as in Example 1 except that the catalyst was prepared using diisobutylphthalate at 0.20 mol per ₂ mol of MgCl, and the analysis results are shown in Table 1 below. Indicated.

Comparative example  3

In Step 3 of preparing the solid titanium catalyst of Example 1, the catalyst was prepared under the same conditions as in Example 1 except that the catalyst was prepared using diethylphthalate at 0.15 mol per ₂ mol of MgCl, and the analysis results are shown in Table 1. It was.

Comparative example  4

In the third step of the solid titanium catalyst of Example 1, the catalyst was prepared under the same conditions as in Example 1 except that the catalyst was prepared using 0.15 mol of ethyl benzoate per ₂ mol of MgCl, and the analysis results are shown in Table 1. It was.

Comparative example  5

The polymerization was carried out under the same conditions as in Example 1, except that 0.7 mmol of cyclohexylmethyldimethoxysilane was used as the external electron donor in the polymerization process of Example 1, and the analysis results are shown in Table 1.

Comparative example  6

The polymerization process of Example 1 was carried out under the same conditions as in Example 1 except that 0.7 mmol of dicyclopentyldimethoxysilane was used as the external electron donor, and the analysis results are shown in Table 1.

Electron donor Donor / MgCl ₂ (mol ratio) DCHDMS (mmol) Polymerization Activity (kgPP / gCat) MI (g / 10min) Molecular Weight Distribution (Mw / Mn) Example 1 DINP 0.11 0.7 36 15.6 6.3 Example 2 DIDP 0.11 0.7 37 16.2 6.6 Example 3 DTDP 0.11 0.7 34 14.8 6.9 Example 4 DINP 0.15 0.7 34 14.5 6.7 Example 5 DINP 0.20 0.7 32 14.7 6.2 Example 6 DIDP 0.15 0.7 35 14.9 6.4 Example 7 DIDP 0.20 0.7 33 15.6 6.4 Example 8 DIDP 0.11 0.35 40 18.5 6.8 Example 9 DIDP 0.11 1.4 34 14.6 6.3 Comparative Example 1 DIBP 0.15 0.7 29 13.5 5.1 Comparative Example 2 DIBP 0.20 0.7 27 10.7 5.0 Comparative Example 3 DEP 0.15 0.7 26 12.6 5.2 Comparative Example 4 EB 0.15 0.7 22 12.8 5.3 Comparative Example 5 DINP 0.11 0.7 ( ^* ) 37 12.6 4.7 Comparative Example 6 DINP 0.11 0.7 ( ^** ) 41 5.8 4.9

Note) (8) below (8) and (**) below (9).

(1) DINP: diisononyl phthalate

(2) DIDP: diisodecyl phthalate

(3) DTDP: dietary decyl phthalate

(4) DIBP: diisobutyl phthalate

(5) DEP: diethyl phthalate

(6) EB: ethyl benzoate

(7) DCHDMS: dicyclohexyldimethoxysilane

(8) CHMDMS: cyclohexylmethyldimethoxysilane

(9) DCPDMS: dicyclopentyldimethoxysilane

The polymer produced by the olefin polymerization or copolymerization method of the present invention has a wide molecular weight distribution by using a catalyst having excellent catalytic activity and hydrogen reactivity and having high stereoregularity, thereby increasing productivity of the polymerization process. .

Claims (5)

An olefin polymerization or copolymerization method characterized by polymerizing or copolymerizing an olefin in the presence of the following (a), (b) and (c): (a) a solid titanium catalyst prepared by the production process comprising the following steps: (1) dissolving a magnesium halide compound in an oxygenated solvent which is a mixed solvent of 3 to 6 carbon atoms contained in the ring and at least one alcohol compound to obtain a magnesium compound solution, (2) The titanium halide compound is added to the magnesium compound solution so that the molar ratio of the oxygenated solvent: titanium halide compound is 1: 3.0 to 10, and the reaction is performed first at -10 to 30 ° C, and then the temperature is increased or aged. To obtain particles, and then adding a titanium halide compound so that the molar ratio of the oxygen solvent: titanium halide compound is 1: 0.3 to 7.0 to prepare a carrier by secondary reaction. (3) reacting the carrier with a phthalic acid dialkyl ester having an alkyl group having 9 to 13 carbon atoms as a titanium halide compound and an electron donor to prepare a titanium supported catalyst, and (4) washing the prepared catalyst with a hydrocarbon solvent at a temperature of 40 ~ 200 ℃; (b) an organoaluminum compound; And (c) An external electron donor which is an organosilicon compound having the general formula of (C ₆ H ₁₁ ) ₂ Si (OR) ₂ , wherein R represents an alkyl group having 1 to 5 carbon atoms. The method for olefin polymerization or copolymerization according to claim 1, wherein the amount of the oxygen-containing solvent in step (1) is 1 to 15 mol per mol of magnesium atom of the magnesium halide compound. The method for olefin polymerization or copolymerization according to claim 1, wherein the titanium halide compound of step (2) is a compound of the following general formula (I). Ti (OR) _a X _(4-a) ‥‥‥ (I) [Where R represents an alkyl group of 1 to 10 carbon atoms, X is a halogen group element, and a is an integer of 0 to 3 to match the valence of the general formula] The olefin polymerization according to claim 1, wherein the phthalic acid dialkyl ester electron donor having an alkyl group having 9 to 13 carbon atoms in step (3) is diisononyl phthalate, diisodecyl phthalate or dietary decyl phthalate. Or copolymerization method. The external electron donor according to claim 1, which is an organosilicon compound having the general formula of (c) (C ₆ H ₁₁ ) ₂ Si (OR) ₂ , wherein R represents an alkyl group having 1 to 5 carbon atoms. An olefin polymerization or copolymerization method characterized by being clohexyldimethoxysilane or dicyclohexyl diethoxysilane.