KR940000410B1 - Process for the preparation of catalyst composition for ethylene polymerization and process for the preparation of ethylene homo and copolymer using same - Google Patents

Abstract

The catalyst composition of formula (I) for polymerization of ethylene is prepd. by diluting the precusor compsn. (II) with inactive carrier; activating by one or more alkyl aluminium compound of formula (III); then treating by halogen bromide cpd. of formula (IV). In formulas, R" is C1-14 aliphatic or aromatic hydrocarbon radical or COR' (R' is C1-14 aliphatic or aromatic hydrocarbon radical); R" is C1-14 aliphatic or aromatic hydrocarbon radical or OR'" (R'" is C1-14 aliphatic or aromatic hydrocarbon radical); X is Cl, Br, I or their mixt.; ED is organic electron donor cpd. selected from alkyl ester of aliphatic acid and aromatic acid, aliphatic cyclid ether or aliphatic ketone; a is 0.5-56; b is 0.1-2; c is 2-116, and d is d'+ +0.33 (d' is 1-33).

Description

Method for preparing catalyst composition for ethylene polymerization and method for preparing ethylene homopolymer or copolymer using same

The present invention provides a method for preparing a catalyst composition for ethylene polymerization which can be represented by the following general formula (I) and an ethylene homopolymer or air having a melt flow rate ratio of 32 to 40 and a density of 0.91 g / cm 3 to 0.97 g / cm 3 It relates to a process for producing coalescing in slurry.

Mg _a Ti (OR) _b X _c Al _d (R ″) _e X ' _f H _g [ED] _h B _i R ^V jX ″ _3i-j (I)

Wherein R is an aliphatic or aromatic hydrocarbon radical having 1 to 14 carbon atoms or COR ', where R' is an aliphatic or aromatic hydrocarbon radical having 1 to 14 carbon atoms, and R '' is 1 to 14 carbon atoms Aliphatic or aromatic hydrocarbon radical with dog or OR ″ ′ where R ″ ′ is an aliphatic or aromatic hydrocarbon radical having 1 to 14 carbon atoms and X is selected from the group consisting of Cl, Br, I and mixtures thereof ED is an organic electron donor compound selected from the group consisting of alkyl esters, aliphatic ethers, cyclic ethers and aliphatic ketones with aliphatic and aromatic acids, a is a number from 0.5 to 56, b is 0, 1 or 2, and c is 2 to 116, d is d '+ 0.33 (where d' is 1 to 33), f is 0 to 1.5, g is 0 or 1, and e is e + f + is a number such that g is 3 and h is within 2 X 'is Cl or OR ", wherein R" and R are aliphatic or aromatic hydrocarbon radicals having 1 to 14 carbon atoms, the same or different, and X "is Cl, Br and mixtures thereof. I is a number from 0.1 to 1, j is 0 or 1i when R ^v is an aliphatic or aromatic hydrocarbon radical, 0, 1i or 2i when R ^v is OR, and H is Hydrogen.

The catalyst composition as formula (I) prepared above is diluted in an inert carrier to prepare the desired final polymer in the present invention.

Example 1

In European Patent Publication No. 0120503, in preparing an ethylene copolymer having a density of 0.91 g / cm 3 or less, a precursor such as the following formula (A) is supported on silica treated with an aluminum compound or mechanically mixed, followed by the following general formula It was activated by using the same promoter as (B).

Mg _m Ti (OR) _n X _p [ED] _q [A]

Al (R ″) _x X ' _e H _f [B]

Wherein R is an aliphatic or aromatic hydrocarbon radical having 1 to 14 carbon atoms or COR 'wherein R' is an aliphatic or aromatic hydrocarbon radical having 1 to 14 carbon atoms, and X is Cl, Br, I or its Selected from the group consisting of mixtures, ED is an electron donor compound, m is 0.5 to 56 preferably 1.5 to 5, n is 0, 1 or 2, p is 2 to 116, preferably 6 to 14 , q is 2 to 85, preferably 3 to 10, X 'is Cl or OR ", R" and R "' are the same or different and are saturated hydrocarbon radicals having 1 to 14 carbon atoms, e is 0 to 1.5, f is 1 or 0 and d + e + f is 3.

To prepare such a composition, TiCl ₃ was used as a titanium compound, MgCl ₂ was used as a magnesium compound, and tetrahydrofuran (THF) was used as an electron donor. Using them to form a precursor of the general formula (A) and impregnated in the anhydrous-treated silica and then Al (C ₂ H ₅ ) ₃ , Al (C ₂ H ₅ ) ₂ Cl, Al ₂ (C ₂ H ₅ ) ₃ Cl ₃ , Al (C ₆ H ₁₃ ) ₃ and the like were used by activating the alkyl aluminum compound as in the general formula (B).

The catalyst composition having such a composition and ethylitrenenorbornene were brought into contact with each other in a reactor supplied with ethylene and a comonomer between C ₃ and C ₈ so as to have an ethylene density of 0.91 g / cm 3 or less and a melt flow rate of 37 to 40 at 50 ° C. A copolymer was obtained. However, in this European Patent Publication No. 0120503, a method of increasing the melt flow rate ratio in an ethylene copolymer having a density of 0.91 g / cm 3 or more is not indicated.

The ethylene copolymer having the physical properties of the patent is a resin called "ultra low density polyethylene" and has a melt flow rate ratio similar to that of the present invention, which is similar in processability but too weak in strength to be processed into a film or the like.

In the present invention, in order to compensate for the weakness of the strength, even if the density is increased to 0.91 g / cm 3 or more, it has the same melt flow rate ratio.

Similar Example 2

Korean Patent Publication No. 87-215 (patent corresponding to US Pat. No. 219,877) describes the general formula (A) of EP 0120503 in the preparation of ethylene copolymers having a density of 0.94 g / cm 3 to about 0.97 g / cm 3. The precursor is supported on an anhydrous silica treated with an aluminum compound or mechanically mixed, and then treated with a boron halide compound as shown in the following general formula (C).

BR _c X ' _3-c [C]

Wherein R is an aliphatic or aromatic hydrocarbon radical having 1 to 14 carbon atoms or COR 'wherein R' is an aliphatic or aromatic hydrocarbon radical having 1 to 14 carbon atoms, and X is Cl, Br, I or Selected from the group consisting of mixtures thereof, c is 0 or 1 when R is an aliphatic or aromatic hydrocarbon, and 0, 1 or 2 when R is OR '. The boron halide compound may be used alone or in combination thereof. Specific examples thereof include BCl ₃ , BBr ₃ , B (C ₂ H ₅ ) Cl ₂ , and B (OC ₂ H ₅ ) Cl ₂ . In particular, BBr ₃ was referred to as a preferred boron compound.

The precursor treated with the boron halide compound contains 0.1 to 1 mole of boron halide compound per mole of electron donor in the precursor composition.

The entire structure treated with the boron halide compound as described above was used by activating an alkyl aluminum compound such as Formula (B) of EP 0120503.

Activation may be partially activated so that the molar ratio of alkyl aluminum compound: titanium compound is 4: 1 to 8: 1 in the catalyst manufacturing process as necessary. Resin polymerized in the same manner as in the Korean Patent Publication No. 87-215 using the catalyst thus prepared has a melt flow rate of 22 to 32 in the resin density range of 0.94 g / cm 3 to 0.97 g / cm 3.

The resin having the physical properties of the patent is called `` high density polyethylene '', and when the resin density is 0.94-0.97 g / cm 3 and melt flow rate ratio 22 to 32, the strength is maintained due to the high density when processing into a film, but the melt flow rate is low, resulting in poor processability. There was a downside.

The present invention provides an improvement for producing an ethylene homopolymer or copolymer having improved strength and processability with a melt flow rate ratio of 32 to 40 in a resin density range of about 0.91 g / cm 3 to 0.97 g / cm 3, which is not disclosed by the above patents. It is an object of the present invention to provide a method for preparing a catalyst composition and a resin polymerization method using the same.

In order to achieve the above object, a method for preparing a catalyst composition which may be represented by the following general formula (I) of the present invention may be obtained by diluting the precursor composition of the general formula (II) with an inert carrier material, and then At least one or more is partially activated with an alkyl aluminum compound and then treated with a boron halide compound of formula (IV).

Mg _a Ti (OR) _b X _c Al _d (R ″) _e X ' _f H _g [ED] _h B _i R _vj X ″ _3i-j (I)

Mg _m Ti (OR) _b Al _0.33 X _c [ED] _h (II)

Al _d '(R'') _e X' _f H _g (III)

B _f R _vj X ' _3-j (IV)

Wherein R is an aliphatic or aromatic hydrocarbon radical having 1 to 14 carbon atoms or COR 'wherein R' is an aliphatic or aromatic hydrocarbon radical having 1 to 14 carbon atoms, and R '' is 1 to 14 carbon atoms Is an aliphatic or aromatic hydrocarbon radical having a dog or OR ″ ′ (where R ″ ′ is an aliphatic or aromatic hydrocarbon radical having 1 to 14 carbon atoms) and X is selected from the group consisting of Cl, Br, I and mixtures thereof ED is an organic electron donor compound selected from the group consisting of alkyl esters, aliphatic ethers, cyclic ethers and aliphatic ketones with aliphatic and aromatic acids, a is a number from 0.5 to 56, b is 0, 1 or 2, and c is 2 to 116, d is d '+ 0.33 (where d' is 1 to 33), f is 0 to 1.5, g is 0 or 1, and e is e + f + is a number such that g is 3 and h is within 2 And X 'is Cl or OR ", wherein R" and R are aliphatic or aromatic hydrocarbon radicals having 1 to 14 carbon atoms, the same or different, and X "is Cl, Br and mixtures thereof. I is a number from 0.1 to 1, j is 0 or 1i when R ^v is an aliphatic or aromatic hydrocarbon radical, 0, 1i or 2i when R ^v is OR, and H is Hydrogen.

A method for preparing a more specific catalyst composition of the present invention is obtained by dissolving at least one magnesium compound having the formula (V) and at least one titanium compound having the formula (VI) in at least one liquid organic electron donor compound. In this electron donor compound, a solution of the precursor composition having the general formula (II) is formed, the precursor composition is diluted with an inert carrier, and then partially activated with at least one alkyl aluminum compound of the general formula (III). And then treated with a boron halide compound of formula (IV).

MgX ₂ (V)

Ti _w (OR) _x Al _y X _z (VI)

Wherein R is an aliphatic or aromatic hydrocarbon radical having 1 to 14 carbon atoms or COR 'wherein R' is an aliphatic or aromatic hydrocarbon radical having 1 to 14 carbon atoms, w is 1, x is 0 , 1 or 2, y is 1/3, z is 2 to 116, X is selected from the group consisting of Cl, Br, I and mixtures thereof.

In addition, in order to achieve another object of the present invention, the resin polymerization method of the present invention is a mixture of ethylene and at least one alpha olefin having 3 to 8 carbon atoms with ethylene or a carbon atom and a pressure of 2,000 psi or less. , At a temperature of about 80 to about 90 ° C., and reacting on a slurry in the presence of a suitable hydrogen so that the melt index is within about 0.01 g / 10 minutes to about 100 g / 10 minutes, preferably from about 0.01 g / 10 minutes to about 10 g / 10 minutes. A high load melt index of about 20 g / 10 minutes to about 2,000 g / 10 minutes, preferably 20 g / 10 minutes to 1,000 g / 10 minutes, and a melt flow rate ratio of about 22 to 42, preferably about 32 to About 40 and having a resin density of from about 0.91 g / cm 3 to about 0.97 g / cm 3.

Catalyst manufacturing

In accordance with the invention, the melt index is less than about 0.01 g / 10 minutes to about 100 g / 10 minutes, preferably less than about 0.01 g / 10 minutes to about 10 g / 10 minutes, and the high load melt index is about 2,000 psi or less. 20 g / 10 min to about 2,000 g / 10 min, preferably 20 g / 10 min to 1,000 g / 10 min, melt flow rate ratio is about 22 to 42, preferably about 32 to about 40, and resin density is about 0.91 Catalytic precursor compositions for use in polymerizing resins of g / cm 3 to about 0.97 g / cm 3 form precursor compositions with magnesium compounds, titanium compounds and electron donor compounds and dilute the prestructural material with an inert carrier, Partially activating the electrical composition with an alkyl aluminum compound, and then treated with a boron halide compound.

Among the catalysts prepared in the above-mentioned Korean patent, the catalyst used only by treating with BBr ₃ and activated in the reactor was found to be agglomerated with particles of resin produced when polymerized on a slurry of normal hexane solution. However, by using the catalyst treated with the boron halide compound after partial activation of the catalyst precursor in advance as in the present invention, such a phenomenon can be eliminated to obtain resin powder particles having good flowability and uniform size.

Catalyst precursor composition

In particular, the present invention is characterized by using TiCl ₃ .1 / 3AlCl ₃ as a titanium compound to obtain a stable catalyst composition.

By using this material, it can be dissolved in tetrahydrofuran, an electron donor at the same time, with anhydrous MgCl ₂ , eliminating the hassle of precursor preparation and precisely controlling the molar ratio of titanium compound and magnesium compound. That is, TiCl ₄ is decomposed to release HCl, which makes it difficult to control and difficult to quantify.

When the titanium compound and the magnesium compound are completely dissolved in tetrahydrofuran, the solution is dehydrated at 600 ° C. in advance, impregnated with silica treated with aluminum alkyl, and then dried under a nitrogen atmosphere to form a catalyst fluid having good fluidity.

At least one catalyst precursor composition impregnated with silica must first be treated with an alkyl aluminum compound, wherein the molar ratio of the alkyl aluminum compound and the titanium compound in the precursor composition is less than or equal to 4: 1, preferably less than or equal to 0.1. : The molar ratio of the electron donor compound and the aluminum compound when the treatment with the at least one alkyl aluminum compound is partially activated to 1: 0.325 or more. do. The catalyst composition thus treated with an alkyl aluminum compound and then dried under a nitrogen atmosphere exhibits a good fluidity.

As described above, when the catalyst precursor treated with the at least one alkyl aluminum compound is treated with the boron halide again, the molar ratio of the boron halide compound and the electron donor compound in the catalyst precursor is 0.1: 1 to 0.7: 1. To be The catalyst composition finally isolated with a boron halide compound becomes a powder having good fluidity when dried under a nitrogen atmosphere.

The reason for the limitation of the above range is to produce a resin having a melt flow rate ratio desired in the present invention only within this range.

Activation of the catalyst precursor composition

Since the catalyst precursor composition prepared by the above method is very insignificant even if there is little or no activity, the polymerization is activated with at least one alkyl aluminum compound in the reactor. At this time, the alkyl aluminum compound used is the same as or different from the alkyl aluminum compound used in the partial activation step, and when the reactor is injected, it is injected by diluting in an inert solvent to an appropriate concentration as necessary.

Polymerization

In a 2 liter capacity commercial laboratory reactor using the catalyst composition prepared in the present invention, between ethylene and at least one C ₃ to C ₈ under a pressure of up to 2000 psi and a temperature of about 80 ° C. to about 90 ° C. Density from about 0.91 g / cm 3 to about 0.97 g / cm 3 in the presence of a comonomer and hydrogen, the normal melt is 0.01 g / 40 to 10 g / 10 minutes, and the high load melt is about 20 g / 10 minutes to about 1,000 g Ethylene homopolymers or copolymers having a melt flow rate ratio of about 22 to 42, preferably about 32 to about 40, at / 10 minutes can be obtained.

Suzy

The density of ethylene homopolymers or copolymers decreases gradually with increasing amounts of comonomers. The amount of comonomer required to obtain the same result varies according to the comonomer molecular weight under the same conditions. In order to obtain the same result in a copolymer having a predetermined density and a predetermined melt index, C ₃ > C ₄ > C ₅ > C ₆ > More molar amounts of comonomer are required in order of C ₇ > C ₈ .

Examples of comonomers that can be used include propylene, butene-1, pentene-1, hexene-1, 4-methyl, pentene-1, heptene-1 and octene-1.

The flow index of the melt index increases with the addition of more hydrogen with the partial pressure of hydrogen. The following examples are intended to illustrate the method and do not limit the scope of the invention.

The properties of the polymers prepared in the examples are measured by the following test methods.

Melt index (MI) ... measured at 190 ° C in accordance with ASTM D-1238 Condition E and reported in g / 10 min.

Flow index (HLMI) ... Measure 10 times the weight used for melt index measurement in accordance with ASTM D-1238 Condition F.

Example 1

Immersion of supported materials into supporting materials

In a 20 liter four-necked round bottom flask equipped with a circulating chiller and a stirrer, about 400 g of silica dried at 600 ° C. for at least 12 hours was slurried in about 8 liters of anhydrous normal hexane, and then triethyl aluminum diluted in normal hexane. 1 molar solution is added at least 0.5 cc.

Drying with nitrogen at about 45 ° C. for about 30 minutes yields a dry powder (average particle size 40 μm) with good flowability. The silica used above had a surface area of 20 to 500 m 2 / g and an average pore size of 10 to 300 mm 3.

In a 20-liter four-neck round bottom flask equipped with a circulating chiller and a stirrer, about 40 g of MgCl ₂ , about 32 g of TiCl ₃ · 1 / 3AlCl ₃ , and 8 liters of anhydrous tetrahydrofuran were added and stirred at about 65 ° C. for about 30 minutes. To dissolve completely. The completely dissolved solution is added to the previously prepared dry silica powder and dried at about 45 ° C. for at least about 30 minutes to obtain a free flowing powder.

Example 2

Partial activation of precursors

The precursor-impregnated silica prepared according to Example 1 was slurried in 8 liters of normal hexane in a four-necked round bottom flask as in Example 1, and the electron donor in the precursor impregnated on silica and the alkyl aluminum compound The molar ratio of aluminum is 1: 0.3. The used hexane is dried in the same manner as in Example 1 to obtain a powder with good flowability.

Example 3

Boron trichloride treatment of partially activated precursors

The precursor composition in which the precursor of Example 1 was partially activated according to Example 1 was slurried in 8 liters of normal hexane in a four-necked round bottom flask as in Example 2, and the electron donor in the precursor impregnated with silica The molar ratio of boron trichloride should be about 1: 0.4. The mixture is dried with nitrogen for at least about 30 minutes while being washed with nitrogen to obtain a dry powder having a silica particle size.

EXAMPLES 4-11

The eight examples detailed below are examples of polymerization using an experimental 2-liter autoclave.

In each polymerization, the molar ratio of ethylene and hydrogen is 2: 1 to 8: 1, and the comonomer of butene-1 is added in an amount of 0 to 15 g, and the polymerization is performed at 90 ° C. for at least 30 minutes.

In Examples 4 to 7, the molar ratio of Al: Ti is 4: 1 during partial activation.

TABLE 1

In Examples 8 to 11, unlike in Examples 4 to 7, the partial activation ratio is set to Al: Ti of 1.1: 1 and the other conditions are the same.

TABLE 2

Claims (9)

After diluting the precursor composition of formula (II) with an inert carrier material, at least one or more of formula (III) is partially activated with an alkyl aluminum compound and then treated with a halogenated boron compound of formula (IV) A process for producing a catalyst composition for ethylene polymerization, which may be represented by the following general formula (I): Mg _a Ti (OR) _b X _c Al _d (R ″) _e X ' _f H _g [ED] _h B _i R _vj X ″ _3i-j (I) Mg _a Ti (OR) _b Al _0.33 X _c [ED] _h (II) Al _d '(R'') _e X' _f H _g (III) B _f R ^v _j X ″ _3-j (IV) Wherein R is an aliphatic or aromatic hydrocarbon radical having 1 to 14 carbon atoms or COR ', where R' is an aliphatic or aromatic hydrocarbon radical having 1 to 14 carbon atoms, and R '' is 1 to 14 carbon atoms Is an aliphatic or aromatic hydrocarbon radical having a dog or OR ″ ′ (where R ″ ′ is an aliphatic or aromatic hydrocarbon radical having 1 to 14 carbon atoms) and X is selected from the group consisting of Cl, Br, I and mixtures thereof ED is an organic electron donor compound selected from the group consisting of alkyl esters, aliphatic ethers, cyclic ethers and aliphatic ketones with aliphatic and aromatic acids, a is a number from 0.5 to 56, b is 0, 1 or 2, and c is 2 to 116, d is d '+ 0.33 (where d' is 1 to 33), f is 0 to 1.5, g is 0 or 1, and e is e + f + is a number such that g is 3 and h is within 2 Is a number of 85, X 'is Cl or OR ", wherein R" and R are aliphatic or aromatic hydrocarbon radicals having 1 to 14 carbon atoms, the same or different, and X "consists of Cl, Br and mixtures thereof I is a number from 0.1 to 1, j is 0 or 1i when R ^v is an aliphatic or aromatic hydrocarbon radical, 0, 1i or 2i when R ^v is OR, and H is hydrogen to be. The method according to claim 1, wherein at least one magnesium compound having the formula (V) and at least one titanium compound having the formula (VI) are dissolved in at least one liquid organic electron donor compound to A solution of the precursor composition having formula (II) is formed, the precursor composition is diluted with an inert carrier, and then partially activated with at least one alkyl aluminum compound of formula (III), and then A process for producing a catalyst composition for ethylene polymerization which can be represented by the following general formula (I), which is treated with a boron halide compound of (IV). MgX ₂ (V) Ti _w (OR) _x Al _y X _z (VI) Wherein R is an aliphatic or aromatic hydrocarbon radical having 1 to 14 carbon atoms or COR 'wherein R' is an aliphatic or aromatic hydrocarbon radical having 1 to 14 carbon atoms, w is 1, x is 0 , 1 or 2, y is 1/3, z is 2 to 116, X is selected from the group consisting of Cl, Br, I and mixtures thereof. The method of claim 1 or 2, wherein the precursor composition is prepared from TiCl ₃ .1 / 3AlCl ₃ , anhydrous MgCl ₂ and tetrahydrofuran. The molar ratio of the alkyl aluminum compound and the titanium compound in the precursor composition when partially activating the precursor composition of the general formula (II) diluted with the inert carrier material is the general formula (III). Method for producing a catalyst composition, characterized in that 1 or less. The method of claim 4, wherein the molar ratio is less than 2: 1 0.1: 1. The molar ratio of the electron donor compound and the aluminum compound according to claim 1 or 2, when the precursor composition of the general formula (II) diluted with the inert carrier material is partially activated by the general formula (III). Method for producing a catalyst composition, characterized in that 0.325 or more. The method according to claim 1, wherein the molar ratio of the boron halide compound and the precursor compound in the catalyst precursor is reduced when the catalyst precursor material partially activated by the general formula (III) is again treated with the halogen compound of the general formula (IV). A method for producing a catalyst composition, characterized in that 0.1: 1 to 0.7: 1. A mixture of ethylene with at least one alphaolefin having from 3 to 8 carbon atoms is combined with a catalyst composition prepared by any one of claims 1 to 7 and a pressure of up to 2000 psig, from about 80 ° C. to about 90 ° C. And reacting in slurry phase in the presence of suitable hydrogen. The method of claim 8, wherein the melt flow rate ratio of the ethylene homo polymer or copolymer is 32 to 40 and the density is 0.91 to 0.97 g / cm 3.