KR810001467B1 - Process for polymerization of -oleffins - Google Patents

Abstract

α-Olefins were polymd. stereoregularly by catalysts containing organoaluminum compds., carboxylates or their complexes with Ti halides, and a carrier prepd. by grinding Mg halides, ortho carboxylic acid ester (I; R1 = aromatic hydrocarbon radical; R2,R3,R4 = hydrocarbon radical) and aluminum halideorganic acid ester, and heating with TiCl4.

Description

Polymerization Method of α-olefins

TECHNICAL FIELD This invention relates to the stereospecific polymerization method of (alpha) -olefins, and its catalyst.

It is already known that α-olefins such as propylene and butenes polymerize in the presence of so-called Ziegler-Natta catalysts which constitute titanium trichloride and organoaluminum compounds to form stereospecific polyα-olefins. It is carried out commercially. Recently, in order to improve the activity of the catalyst, a method of maintaining the titanium component in the Ziegler-Natta catalyst on a carrier has been developed and generally used as a catalyst for ethylene polymerization.

When polymerizing α-olefins such as propylene and butene, a crystalline polymer can be obtained if the polymer chain does not have an isotactic structure in which an alkyl group such as methyl or ethyl is stericly controlled. none.

Therefore, the catalyst which improves only polymerization activity like the case of superposing | polymerizing ethylene cannot be regarded as a useful storage medium in superposition | polymerization of (alpha) -olefins.

In addition, controlling the stereospecificity of the polymer is significant from the technical point of view.

In this regard, a process in which an electron donating compound is added as a third component to a combination of a carrier which improves the stereospecificity of the polymer by forming a titanium compound and an organoaluminum compound supported by the titanium component on the magnesium halide. It provided a method for configuring.

As an example, British Patent No. 1,387,890 discloses that a catalyst consists of a titanium halide composition, an organoaluminum compound and an electron donating compound, and the titanium halide composition is used to grind the magnesium halide together with the titanium halide, or a composite of the titanium halide and the electron donating compound. It is mentioned that it is prepared by grinding with magnesium halide.

However, these catalysts are still insufficient in polymerization activity and crystallinity of the obtained polymer.

Accordingly, an object of the present invention is to provide a stereospecific polymerization method of α-olefins to obtain a high stereospecific polymer having high polymerization activity.

It is still another object of the present invention to provide a poly alpha -olefin which is provided as a carrier of the titanium catalyst component to improve polymerization activity and stereospecificity.

The above object of the present invention is the presence of a catalyst constituting a titanium component obtained by contact treatment with a product which is co-milled with magnesium halides and aromatic allotonic acid esters, titanium halides, organic aluminum compounds and electron donating compounds. Basically achieved by polymerizing α-olefins under the following conditions.

More specifically, the present invention is characterized in that in the presence of a catalyst constituting a titanium component obtained by contact treatment of a product obtained by co-milling a magnesium halide, an aluminum halide and an aromatic olto carbonate ester with a titanium halide organoaluminum compound and an electron donating compound Stereospecific polymerization of α-olefins can be carried out.

More specifically, the product obtained by subjecting magnesium halide, aluminum halide organic acid ester composite and aromatic olto carboxylic acid ester co-pulverized product with titanium halide to obtain titanium component as a titanium component carrier for polymerization catalyst of α-olefins Can be used.

In another embodiment of the present invention, a titanium component obtained by contact treatment of a titanium halide with a magnesium halide, an aluminum halide, an aromatic olto carboxylic acid ester, and a product of co-pulverizing an organosilicon compound having at least one alkoxy group with a titanium halide is used as an α-olefin. It can be used as a titanium component carrier for a polymerization catalyst.

Magnesium halides used in the production of titanium component carriers are actually more preferred anhydrous magnesium halides, particularly preferably magnesium chloride.

The aromatic allocarbon acid ester used here is represented by the following general formula.

Wherein R ¹ is an aromatic hydrocarbon group and each of R ² , R ³ and R ⁴ , which is the same or different, is a hydrocarbon group.

Preference is given to using allo benzoic acid esters or derivatives of allo naphthoic acid.

In R <^2> , R <^3> and R <^4> , a C1-C10 aliphatic hydrocarbon group is preferable.

Examples of these compounds include methyl olto benzoate, ethyl olto benzoate, methyl olto toluate, ethyl olto toluate, ethyl olto aniseate, and propyl olto aniseate. The use of aromatic oltocarbonates is a feature of the present invention and the effect of requirements can not be achieved as in Examples 3 and 6 below using aliphatic oltocarbonates. The amount of the aromatic allotonic acid ester is preferably 0.05 to 0.3 mol per 0.1 mol of the magnesium halide or is not particularly limited.

The aluminum halides used to prepare the activated titanium catalyst component are actually preferably anhydrous aluminum halides, but particularly preferably aluminum chlorides.

The amount of the aluminum halide is more preferably 0.5 to 2.0 moles per 1.0 mole of the aromatic oltocarboxylic acid ester, but is not particularly limited.

In addition, the aluminum halide-organic acid ester composite aluminum halide used for producing the activated titanium catalyst component is obtained by a conventional method by mixing with an organic acid ester at a real or high temperature.

The organic acid ester used here is aromatic carboxylic acid ester, aliphatic carboxylic acid ester, and alicyclic carboxylic acid ester.

Aromatic carboxylic acid esters are more preferred, and examples thereof include methyl benzoate, ethyl benzoate, methyl toluylate and the like.

The amount of the composite is more preferably 0.05 to 0.3 moles per 1.0 mole of magnesium halide, but is not particularly limited.

Furthermore, the organosilicon compound having at least one alkoxy group used for producing the activated titanium component is represented by the following general formula.

Si (OR ⁵ ) m ^x n ^y p

Wherein R ⁵ is an alkyl group and each X and Y is a hydrocarbon group, halogen or carboyl oxy group

(여기서 R은 알킬기임)이고, m은 1-4의 정수, n 및 p는 0-3이며 m,n 및 p의 합계가 4이다.

(Where R is an alkyl group), m is an integer of 1-4, n and p are 0-3 and the sum of m, n and p is 4.

Examples of these compounds include Si (OC ₂ H ₅ ) ₃ Cl, Si (OC ₂ H ₅ ) ₂ Cl ₂ , Si (OCOCH ₃ ), (OC ₂ H ₅ ) Cl ₂ , Si (OC ₂ H ₅ ) ₄ , Si (C ₂ H ₅ ) ₂ , (OC ₂ H ₅ ) ₂ , Si (C ₆ H ₅ ) (OC ₂ H ₅ ) _3, and the like.

Where Si (O ₂ H ₅ ) (OC ₂ H ₅ ) ₃ , Si (OC ₂ H ₅ ) ₄ , Si (C ₂ H ₅ ) ₂ (OC ₂ H ₅ ) ₂ or Si (C ₆ H ₅ ) ( Particularly preferred are compounds having at least two alkoxy groups, such as OC ₂ H ₅ ) ₃ .

The amount of the organosilicon compound is preferably 0.05 to 0.15 moles per 1.0 mole of magnesium halide, but is not particularly limited.

Combinations of magnesium halides and aromatic allocarboxylic acid esters (1), combinations of magnesium halides, aluminum halides and aromatic allocarboxylic acid esters (2), magnesium halides, aluminum halide-organic acid ester complexes The co-milled product of the combination (3) of the aromatic allotonic acid ester, or the combination (4) of the magnesium halide, aluminum halide, the aromatic alto carbonate ester and the organosilicon compound having at least one alkoxy group is first constituted. In this case, a reaction product of an aluminum halide having an aromatic altocarboxylic acid ester already synthesized or a magnesium halide having an aromatic altocarboxylic acid ester already synthesized may be used instead of separately adding to each component.

The grinding process is carried out in a vacuum or inert gas state and is effective in the absence of oxygen and moisture.

Grinding treatment conditions are generally configured between 0 ° and 80 ° C but are not particularly limited.

The grinding time varies depending on the type of grinder, but it is normal to be between 2 hours and 100 hours.

Next, the co-milled product thus obtained is subjected to contact treatment with the titanium halide.

Examples of the titanium halides used include titanium tetrachloride, titanium tetra bromide and the like.

In particular, titanium tetra chloride is more preferred. Suspended pore-pulverized product in a titanium halide or titanium halide solution of an inert solvent to maintain contact at a temperature of 0 ~ 135 ℃ and then contact treatment can be easily carried out by separating the solid material, washed with an inert solvent to free glass titanium The halide is removed or dried to obtain an activated titanium catalyst component.

By inert solvent is meant here an aliphatic, cycloaliphatic or aromatic hydrocarbon and mixtures thereof.

The activated titanium component obtained above according to the present invention combines an organic aluminum compound and an electron donor compound to form a catalyst having high activity in the polymerization of α-olefins.

The organoaluminum compound used here is represented by the following general formula.

AlRmX'3-m

R is a hydrocarbon group, X` is an alkoxyl group, hydrogen or a halogen atom, and m is 1.5-3.0.

Representative examples include triethyl aluminum, tri-n-butyl aluminum, tri-iso-butyl aluminum, tri-n-hexyl aluminum, diethyl aluminum monochloride, diethyl aluminum hydride, thiethyl aluminum ethoxide and the like. have.

These may be used alone or in mixtures.

The molar ratio of the organoaluminum compound to the titanium metal of the activated titanium component is preferably in the range of 1 to 500, but is not limited thereto.

Electron-donating compounds used include phosphorus, oxygen, or nitrogen-containing compounds.

The phosphorus-containing compound is represented by the following general formula.

P (Z ¹ ) m (Y'Z ') ₃ -m or O = P (Z') m (Y'Z ') ₃ -m

Here, Z 'is a hydrogen atom, a hydrocarbon group amino group or an alkyl amino group, Y' is an oxygen or sulfur atom, m is 0-3.

The oxygen-containing compound is represented by the following general formula.

Wherein Z ² and Z ³ may each be a hydrocarbon group or may together form a ring and K is 1 to 3.

Examples of the nitrogen-containing compound include amines or derivatives thereof. It is preferable that organic acid esters and aromatic olto carboxylic acid esters having the above general formula be used as the electron donating compound. Representative examples of organic acid esters are methyl formate, ethyl acetate, methyl benzoate, ethyl benzoate, methyl toluylate, methyl aniseate and others.

The electron donating compound is in contact with other components at any time during the preparation of the catalyst.

The electron donating compound may also be added when the? -olefins are polymerized. In general, a method of contacting an activated titanium component with an organoaluminum compound and then contacting an electron donor compound, a method of contacting an organoaluminum compound with an electron donor compound and then contacting an activated titanium component, and electron donating an activated titanium component There is a method of contacting the compound and then contacting the organoaluminum compound or simultaneously contacting three components.

It is particularly preferred to have some or all of the activated titanium component present as an electron donating compound added when contacting the organoaluminum compound to polymerize the polymerizable monomer. The amount of the electron donating compound is preferably in the range of 0.1 to 0.5 moles per 1.0 mole of the organic aluminum compound, and when the amount exceeds 0.5 moles, the result is an abrupt decrease in polymerization activity without an increase in stereospecificity.

The present invention can be applied to homopolymerization or copolymerization of α-olefins having the following general formula.

R ₁ -CH = CH ₂

Here, R ₁ is a copolymer of an alkyl group having 1 to 10 carbon atoms or ethylene and the above α-olefin.

Examples of the α-olefins are propylene, butene-1, hexane-1,4-methyl-pentene-1 and the like.

The polymerization process according to the present invention can be carried out by a conventional method using conventional conditions.

The polymerization temperature is generally in the range of 0 to 100 ° C, preferably 20 to 90 ° C, and the pressure is in the range from atmospheric pressure to 50 atm, preferably from atmospheric pressure to 40 atm.

In the polymerization reaction, solvents such as aliphatic, alicyclic or aromatic hydrocarbons or mixtures thereof can be used, for example propane, butane, pentane, hexane, heptane, cyclohexane, benzene, toluene or mixtures thereof.

Moreover, it can use for block polymerization using the liquid monomer itself as a solvent.

Alternatively, the polymerization may be carried out on water vapor in which the gaseous monomers are in direct contact with the catalyst without using a solvent.

The molecular weight of the polymer produced by the process of the present invention varies depending on the reaction method, type of catalyst and polymerization conditions.

However, the molecular weight can be adjusted by addition to the reaction system such as hydrogen, alkyl halides and dialkyl zinc.

The present invention is illustrated by the following examples, and reference examples outside the scope of the present invention are shown for comparison.

Example 1

(A) Under a nitrogen atmosphere, 20.0 g of magnesium chloride and 6 ml of methyl olto benzoate were added to a vibratory grinder having a pot of 600 ml of internal volume, and 80 mill balls of 12 mm in diameter were placed and ground for 20 hours.

10 g of the pulverized product thus obtained and 200 ml of titanium chloride were added to a 300 ml round bottom flask, stirred at 80 ° C. for 2 hours, and the surface solution was removed by a gradient method.

Next, the mixture was washed several times at room temperature with stirring with 200 ml of n-heptane, and then the surface solution was removed by a gradient method, and 200 ml of n-heptane was further added to obtain a slurry of activated titanium.

A portion of the activated titanium component slurry was taken and n-heptane was evaporated and analyzed.

The content of activated titanium component was 1.5% by weight.

(B) 1.0 L of n-heptane, 0.1 g of activated titanium component, 0.375 ml of triisobutyl aluminum, 0.18 ml of diethyl aluminum chloride and 0.08 ml of methyl oltobenzoate were charged to a high pressure section of a capacity of 3.0 L under nitrogen atmosphere.

Nitrogen gas was discharged from the high pressure part with a vacuum pump, and then gaseous hydrogen was charged to a partial pressure of 0.1 Kg / cm ² .

Then, propylene is charged up to ² Kg / cm ² gauge of water vapor pressure. The internal pressure was raised to 70 ° C. after 5 minutes by heating the high pressure portion. The polymerization was continued at 70 ° C. for one hour while charging propylene while maintaining a pressure of ⁵ Kg / cm ² gauge.

After cooling the high pressure portion, unreacted propylene was removed, and the contents were removed, filtered, and dried at 60 캜 reduction. Thus, 85.4 g of white powdery polypropylene was obtained.

Limit viscosity (135 ℃, Tetralin): 1.98

Apparent Density: 0.33g / ml

The remaining amount of the polymer extracted by boiling n-heptane (powder II): 92.7%. On the other hand, 4.8 g of a polymer that could be dissolved in n-heptane was obtained. The proportion of the residue extracted by boiling n-heptane with respect to the total polymer (called "total II") was 87.8%.

The polymerization activity of the catalyst in this example was 60 Kg / g.Ti.hr (production rate of polymer per gr of activated Ti per hour).

[Reference Examples 1 and 2]

The titanium component was prepared by co-grinding in the same manner as in Example 1 (a) using 26.4 g of magnesium chloride and 3.6 g of titanium tetrachloride.

The polymerization was repeated in the same manner as in Example 1 (b) except that 0.2 g of the titanium component obtained above and 0.1 ml of triethyl aluminum and ethyl benzoate were used as the third component. The results are shown in Table 1.

Reference Example 3

According to the process of Example 1 (a), a titanium component having 2.5% by weight of titanium was obtained by co-milling 20 g of magnesium chloride and 6 ml of ethyl olto acetate, and then washed with n-heptane to react with titanium tetrachloride.

The polymerization was carried out in the same process as in Example 1 (b) using 0.1 g of the titanium component, 0.375 ml of triisobutyl aluminum, 0.18 ml of diethyl aluminum chloride, and 0.08 ml of methyl olto benzoate.

However, no polypropylene was obtained.

Reference Example 4

According to the process of Example 1 (A), 23.6 g of magnesium chloride and 6.4 g of titanium tetrachloride-ethyl benzoate composite were co-milled to prepare a titanium component having a content of 3.0 wt% titanium.

0.20 g of the titanium component and 0.1 ml of triethyl aluminum were polymerized in the same manner as in Example 1 (b). After 2 hours of polymerization, 110 g of powdery polypropylene was obtained.

Powder II: 70.3%

Limit Viscosity: 1.80

Apparent Density: 0.22g / ml

On the other hand, 30.5 g of amorphous polypropylene was obtained from the filtrate.

Total II: 55.0%

Polymerization Activity: 11.7Kg / g.Ti.hr

Polymer yield: 23.4Kg / g.Ti

Reference Example 5

According to the process of Example 1 (a), 24.7 g of magnesium chloride and 5.3 g of ethyl benzoate were co-milled, and then reacted with titanium tetrachloride while washing with n-heptane to obtain a titanium component having a titanium content of 1.21 wt%.

0.20 g of the titanium component and 0.07 ml of triethyl aluminum were polymerized in the same manner as in Example 1 (b) for 2 hours.

218 g of powdered polypropylene and 25 g of polypropylene that can be dissolved in n-heptane were obtained.

Powder Part II: 95.0%

Apparent Density: 0.28g / ml

Limit score: 1.98

Polymerization Activity: 51Kg / g.Ti.hr

Total II: 85.2%

TABLE 1

Example 2

The polymerization was carried out in the same manner as in Example 1 (b), except that ethyl benzoate was used instead of methyl oltobenzoate as the third component added at the polymerization time using the catalyst component obtained in Example 1 (a). The results are shown in Table 2.

[Examples 3 to 6]

Instead of the methylolto benzoate used in the preparation of the activated titanium component in Example 1 (a), various aromatic allocarbonic acid esters were used to prepare the activated titanium component.

Propylene polymerization was carried out in the same manner as in Example 1 (b) using the activated titanium component thus obtained.

The results are shown in Table 2.

Example 7

The polymerization was carried out in the same manner as in Example 1 (b), using 0.1 g of the activated titanium component obtained in Example 1 (a), 0.1 ml of ethyl benzoate and 0.3 ml of diethyl aluminum ethoxide.

The results are shown in Table 2.

TABLE 2

* 1 Aromatic allotonic acid esters added to the active Ti component.

Example 8

(A) Co-pulverization products were obtained in the same manner as in Example 1 (A), except that 20 g of magnesium chloride, 4.8 g of aluminum chloride, and 6 ml of methyl olto benzoate were used for co-pulverization. 10 g of the above pulverized product and 100 ml of titanium tetrachloride were placed in a 200 ml round bottom flask and stirred for 2 hours, and then the surface solution was removed by decantation.

Next, the washing process was repeated several times while stirring with 100 ml of n-heptane at 80 ° C. for 15 minutes, and then the surface solution was removed by decantation and 100 ml of n-heptane was further added to form an active titanium component slurry.

A portion of the active titanium component slurry was taken and analyzed for evaporation of n-heptane.

The titanium content of the active titanium component was 2.20% by weight.

(B) Polymerization was carried out according to the procedure of Example 1 (b) using 50 mg of the above-mentioned active titanium component, 0.375 ml of triisobutyl aluminum, 0.18 ml of thyethyl aluminum chloride and 0.08 ml of methyl olto benzoate. The results are shown in Table 3.

Example 9

An active titanium component was prepared in the same manner as in Example 8 (A), except that 13.2 g of methyl olto benzoate-aluminum chloride composite (1: 1), which was previously synthesized, was used instead of methylolto benzoate and aluminum chloride for grinding. It was.

The titanium content of the catalyst component thus obtained was 1.97 wt%. The polymerization was carried out in the same manner as in Example 1 (b), except that 48 mg of the catalyst component was used.

The results are shown in Table 3.

Example 10

An active titanium component was prepared in the same manner as in Example 8 (a), except that ethylolto benzoate was used instead of methylolto benzoate.

62 mg of the titanium component was polymerized in the same manner as in Example 1 (b).

The results are shown in Table 3.

Example 11

An active titanium component was prepared in the same manner as in Example 8 (A), except that 4.8 g of anhydrous aluminum bromide was used instead of 4.8 g of aluminum chloride for co-grinding.

The titanium content of the active titanium component thus obtained was 2.21 wt%.

The polymerization was carried out in the same manner as in Example 1 (b), except that 50 mg of the active titanium component was used.

The results are shown in Table 3.

Reference Example 6

The catalyst component was synthesized in the same manner as in Example 8 (A), except that 6 ml of methyl olto acetate was used instead of methyl olto benzoate for co-grinding.

The polymerization was carried out in the same manner as in Example 1 (b), except that 52 mg of the catalyst component was used.

However, no polymer was obtained.

TABLE 3

Example 12

(A) Co-grinding product was prepared in the same manner as in Example 1 (A) using 20 g of magnesium chloride, 3.8 g of aluminum chloride-ethyl benzoate composite (1: 1) and 4 ml of methyl olto benzoate for co-grinding. It was.

An active titanium component was prepared in the same manner as in Example 8 (a), except for using 10 g of the above co-grinding product. Titanium content was 2.10 wt%.

(B) The polymerization was carried out in the same manner as in Example 1 (B), using 62 mg of the active titanium component, 0.375 ml of triisobutyl aluminum, 0.24 ml of dimethyl aluminum chloride, and 0.14 ml of ethyl benzoate. The results are shown in Table 4.

Example 13

An active titanium component was prepared in the same manner as in Example 12 using 20 g of magnesium chloride, 11.9 g of aluminum chloride-ethyl benzoate composite (1: 1) and 1.0 ml of methyl olto benzoate for co-milling.

The polymerization was carried out in the same manner as in Example 12 (b), except that 69 mg of the active titanium component was used.

The results are shown in Table 4.

TABLE 4

Example 14

(A) 20 g of magnesium chloride, 5.6 g of aluminum chloride, 4 ml of methylolto benzoate, and 2 ml of tetraethoxysilane were charged to a vibratory grinder used in Example 1 (a) and ground for 40 hours.

Using 10 g of the above ground product, an active titanium component was prepared in the same manner as in Example 8 (A).

Titanium content was 2.23 wt%.

(B) The polymerization was carried out in the same manner as in Example 1 (B), using 65 mg of the titanium component, 0.375 ml of triisobutyl aluminum, 0.24 ml of thyethyl aluminum coolide, and 0.14 ml of ethyl benzoate. The results are shown in Table 5.

Example 15

Example 14, except that 0.08 ml of methyl olto benzoate and 0.18 ml of diethyl aluminum chloride were used instead of 0.14 ml of ethyl benzoate and 0.24 ml of ethyl aluminum chloride, respectively, using the active titanium component obtained in Example 14 (A). The polymerization was carried out in the same manner as in (A).

The results are shown in Table 5.

Example 16

An active titanium component was prepared in the same manner as in Example 14 (A), except that 2 ml of ethyl triethoxy silane was used instead of tetra ethoxy silane for grinding.

Titanium content was 2.20 wt%.

The polymerization was carried out in the same manner as in Example 14 (b), except that 58 mg of the active titanium component was used.

The results are shown in Table 5.

Example 17

An active titanium component was prepared in the same manner as in Example 14 (A), except that 4.0 ml of ethyl olto benzoate was used instead of methyl olto benzoate for grinding.

62 mg of the titanium component was polymerized in the same manner as in Example 14 (b). The results are shown in Table 5.

Example 18

An active titanium component was prepared in the same manner as in Example 14 (A), except that 2 ml of methylolto benzoate and 6 ml of tetraethoxy silane were used for grinding.

Titanium content was 3.2% by weight.

The polymerization was carried out in the same manner as in Example 14 (b), except that 61 mg of the titanium component was used.

The results are shown in Table 5.

Example 19

The polymerization was carried out in the same manner as in Example 14 (b), except that 0.25 ml of ethyl benzoate was used using the titanium component obtained in Example 14 (a).

The results are shown in Table 5.

Reference Example 7

A titanium component having a titanium content of 2.48 wt% was prepared in the same manner as in Example 8 by co-milling 20 g of magnesium chloride and 6 ml of tetraethoxy silane and reacting with titanium tetra chloride while washing with n-heptane.

58 mg of the titanium component, 0.20 ml of ethyl benzoate and 0.5 ml of triethyl aluminum were polymerized in the same manner as in Example 8 (b) for 1 hour.

69 g of powdered polypropylene and 2.1 g of polypropylene soluble in n-heptane were obtained.

Powder: 95.8%

Apparent density: 0.30g / ml

Limit Viscosity: 1.89

Activity: 35Kg / g.Ti.hr

Total II: 93.0%

TABLE 5

Claims (1)

In the presence of a catalyst composed of a titanium compound having a titanium compound, an organoaluminum compound, and an electron donating compound supported on a carrier to form a-olefin, magnesium chloride and an aromatic orthocarbon represented by the following general formula Stereospecificity of α-olefins, characterized in that the co-milled product of the acid ester and the aluminum halide-organic acid ester (aluminum chloride-aromatic carboxylic acid ester) complex is used as a titanium component carrier of the active titanium component obtained by contact treatment with a titanium halide. Polymerization method.

Wherein R ¹ is an aromatic hydrocarbon group and each of R ² , R ³ and R ⁴ , which may be the same or different, is a hydrocarbon group