KR820002155B1 - Method for preducing olefin polymers - Google Patents

Abstract

Solid catalyst components for olefin polymn. are prepd. by treating a trivalent metal halide with a divalent metal hydroxide, oxide, or carbonate, treating a Group IVA or VA metal compd. with this aduct in the presence of a siloxane, and finally treating with 2 transition metal compds.

Description

Preparation of α-olefin polymer

The present invention relates to a process for preparing olefin polymers and to solid catalyst components of the catalysts used therein.

In the present invention, the olefin polymerization or polymer is, in addition to homopolymerization or homopolymerization of α-olefin, other small amounts of α-olefins (including diolefins) and α-olefins copolymerizable with α-olefins; The polymerization or copolymer of is also included.

Conventionally, as a catalyst for α-olefin polymerization such as ethylene, a transition metal compound is fixed on the surface of magnesium compounds such as magnesium chloride, hydroxy magnesium chloride, magnesium hydroxide, magnesium oxide, and an organic aluminum compound. It is well known to use in combination with.

In recent years, it is suitable for the field of extrusion molding and hollow molding. As an olefin polymer, it has a high molecular weight (low melt melt indexes), and Although it is especially required to have good fluidity, the Ziegler catalyst is, for example, by mixing a supported catalyst component and a mixed organic aluminum compound or mixing an olefin polymer having a significantly different molecular weight. It is possible to expand the fluidity to some extent, but it was not practically satisfactory.

As a method of improving the fluidity, a means for expanding the molecular weight distribution has been taken. The olefin polymer having a narrow molecular weight distribution is suitable for injection molding and the like. On the other hand, a polymer having a wide molecular weight distribution is preferable as the polymer used for extrusion molding, hollow molding, or other stretching. When a polymer having a narrow molecular weight distribution is used for hollow molding, the molded product may not be formed due to excessively high extrusion pressure during molding, or may be formed due to the generation of strings or pegs, or melt fracture. The appearance of is markedly damaged. In the case of extrusion molding, the excessive increase in the extrusion pressure, the increase in the instability of the molding, etc. are severely affected, and the product value is significantly reduced. In order to improve these defects, it is necessary to widen the molecular weight distribution of the polymer and to improve the fluidity during molding. The result of the improvement is that the productivity in the molding process can be improved, a molded article having an excellent appearance can be obtained, and the complicated molding process required by the times is possible.

The present inventors have conventionally known trihydric metal halides and hydroxides of divalent metals, oxides, oxides, carbonates, double salts containing them, or hydrates of divalent metal compounds (hereinafter referred to as only divalent metal compounds). Has been studied as a catalyst component of a reaction product (hereinafter referred to as solid product (I)) as a carrier. The solid product obtained by reacting this solid product (I) with one kind of transition metal compound (e.g., titanium tetrachloride) in the transition metal compound of Group 4a or Group 5a is usually used as an organoaluminum compound. As compounding, a practically satisfactory ethylene polymer having a broad molecular weight distribution cannot be obtained. However, the present inventors have found that when two kinds of transition metal compounds are used as a transition metal compound in the preparation of a catalyst component, an ethylene polymer having a broad molecular weight distribution is obtained. It was found that the transition metal compound was selected from two specific groups and used as a solid product for reacting the same, which was effective in expanding the molecular weight distribution while maintaining polymerization activity. Thus, the present invention has been reached.

An object of the present invention is to provide a method for producing an α-olefin polymer capable of obtaining a polymer having a large polymer yield and a wide molecular weight distribution, and a solid catalyst component of the catalyst used therein.

The present invention provides a reaction product (solid product (I)) of a trivalent metal halide with a hydroxide, oxide, carbonate of a divalent metal, a double salt containing these, or a hydrate of a divalent metal compound in the presence of polysiloxane. The transition metal compound of Group 4a or Group 5a containing halogen (Group A) is further obtained from the solid product (II) obtained by reacting the transition metal compound of Group 4a or Group 5a of the periodic table (hereinafter referred to as halogen-containing transition). May be referred to as a metal compound) and (group B) at least 1 from each of the group 4a or 5a transition metal compound (hereinafter sometimes referred to as halogen-free transition metal compound) containing no halogen To prepare an α-olefin polymer characterized by using a catalyst obtained by reacting two or more kinds of transition metal compounds selected from a species with a solid product (III) and an organoaluminum compound. And a solid catalyst component as the solid product (III) as described above.

As the solid product (II) in the present invention, the inventors of the present invention used the compound of the present invention in combination with organoaluminum as a solid catalyst component to polymerize α-olefins (Japanese Patent Application No. 53-21246, 53-21247) In this case, an olefin polymer having a high polymerization activity and a large specific gravity is used, but the molecular weight distribution of the polymer is narrow. However, the two kinds of specific transition metal compounds reacted with each other are used as a solid catalyst component to greatly widen the width of the molecular weight distribution of the polymer.

In preparing an olefin polymerization catalyst, a solid catalyst using a halogen-containing transition metal compound and a polyalkyl titanate (one of halogen-free transition metal compounds) is known. That is, Japanese Patent Application Laid-Open No. 51-100984 shows a catalyst in which a solid (catalyst) and an organometallic compound are combined with a carrier obtained by halogenation with a polyalkyl titanate 릍 halogenating agent (including titanium tetrachloride, etc.) as an essential component. It is becoming. In Japanese Patent Laid-Open No. 52-24292, a solid obtained in the same manner as in the above-mentioned Japanese Patent Laid-Open No. 51-100984, a solid obtained by contacting various solids (carriers) containing magnesium with a halogen compound of titanium, an organoaluminum compound, The catalyst which compounded is proposed.

The present invention provides a solid product obtained by reacting at least a solid product (I) obtained by reacting a trivalent metal halide and a divalent metal compound in the presence of a polysiloxane in a solid product (II). ) Is itself different from the point of using a solid having a high polymerization activity as a carrier.

The present invention will be described in more detail below.

Examples of the trivalent metal halide include aluminum chloride (anhydrous) and iron trichloride (anhydrous).

As the divalent metal compound, for example, Mg (OH) ₂ , Ca (OH) ₂ , Ba (OH) ₂ , Zn (OH) ₂ , Mn (OH) ₂ , Fe (OH) ₂ , Co (OH) ₂ , oxides of divalent metals such as Ni (OH) ₂ and ground hydroxides, MgO, CaO, BaO, ZnO, MnO, FeO and ground oxides, MgAl ₂ O ₄ , Mg ₂ SiO ₄ , Mg ₆ MnO ₈ Containing complex oxides, MgCO ₃ , CaCO ₃ , BaCO ₃ , MnCO ₃ and ground carbonate, SnCI ₂ · 2H ₂ O, MgCl ₂ · 6H ₂ O, NiCI ₂ · 6H ₂ O, MnCl ₂ · 4H ₂ O, Halide hydrates such as KMgCI ₂ , 6H ₂ O, hydrides of complex compounds as oxides and halides, such as 3MgO MgCI ₂ 4H ₂ O, containing oxides of 3MgO 2SiO 2 2H 2 O and ground divalent metals Hydrates of complex oxides, hydrates of complex compounds consisting of carbonates and hydroxides such as ₃ MgCO ₃ · Mg (OH) ₂ · 3H ₂ O and divalent metals such as Mg ₆ AI ₂ (OH) ₁₆ CO ₃ · 4H ₂ O The hydrate of the hydroxide containing hydroxide etc. are mentioned.

In order to make a trivalent metal halide react with a divalent metal compound, it is preferable to mix and grind | pulverize for 5-100 hours as a bor mill or 1-10 hours as a vibration mill beforehand, and to make it fully mixed. When the mixing ratio is expressed by the atomic ratio of the divalent metal to the trivalent metal, 0.05-20 is usually sufficient, preferably in the range of 0.1-5.0.

The reaction temperature is usually 20-500 ° C, preferably 50-300 ° C. The reaction time is sufficient for 30 minutes-50 hours. In this way, the solid product (I) is obtained.

Subsequently, the solid product (I) is reacted with a transition metal compound in the presence of polysiloxane, washed with a solvent to remove the unreacted transition metal compound and plysiloxane, and dried to obtain a solid product (II).

Examples of the polysiloxane to be used, the general formula - A _{- [Si (R 1, R} 2) -O-] siloxane polymer of a chain (鎖狀) or cyclic (環狀) represented by the n- (n = 3-1,000), For example, as the chain, dimethyl polysiloxane, methyl ethyl polysiloxane, and the like are monoalkyl monoaryl polysiloxanes such as dialkyl polysiloxane, methylphenyl polysiloxane, diaryl polysiloxanes such as diphenyl polysiloxane, hydrogenated polysiloxanes such as hydrogenated methyl polysiloxane, hydrogenated phenyl polysiloxane, and the like. As the cyclic siloxane polymer, octamethylcyclotetrasiloxane, octaethylcyclotetrasiloxane, hexaphenylcyclotrisiloxane and the like can be given.

Examples of the transition metal compound include titanium, vanadium halides, oxyhalides, alcoholates, alkoxy halides, acetoxy halides, and the like. For example, titanium tetrachloride, tetrahedral titanium, tetraethoxytitanium, tetraisopropoxytitanium, Dichlorodiisopropoxytitanium, trichloromonoisopropoxytitanium, trichloromonoisopropoxytitanium, dichlorodibutoxytitanium, vanadium tetrachloride, oxy vanadium trichloride, triisopropoxyvananadyl, tributoxyvana Deals, etc.

As a specific method of reacting the transition metal compound with the solid product (I) in the presence of polysiloxane,

(1) The solid product (I), polysiloxane, and transition metal compound are mixed at the same time and heated.

(2) The solid product (I) and polysiloxane are mixed and then heated with the transition metal compound.

(3) The polysiloxane and the transition metal compound are mixed, and the solid product (I) is added thereto and heated.

(4) A manufacturing method such as the solid product (I) and the transition metal compound is mixed, followed by heating by adding polysiloxane.

In the catalyst preparation of the present invention, as a solvent used during the reaction or after the reaction, aliphatic hydrocarbons such as hexane, heptane, octane, nonane, decane, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, chloro Halogenated aromatic hydrocarbons, such as benzene, dichlorobenzene, and trichlorobenzene, halogenated hydrocarbons, such as carbon tetrachloride, chloroform, dichloroethane, trichloroethylene, tetrachloroethylene, and tetrafluorocarbon, etc. are mentioned.

The mixing ratio of the solid product (I), the polysiloxane and the transition metal compound is 10-10,000 g, preferably 20-1,000 g, and the transition metal compound 1-1,000 g, with respect to 100 g of the solid product (I). The following is 10 g-500 g, and the transition metal compound is 10-1,000 g, preferably 30-500 g with respect to 100 g of polysiloxane.

Although it is not necessary to use a solvent in the mixing and reaction of each said component in order to prepare solid substance (II), it is preferable for uniform reaction.

In this case, any or all of the above components are dissolved or dispersed in a solvent separately beforehand and mixed. The total amount of the solvent used is sufficient to be about 10 times or less of the total amount of each component.

The temperature for mixing is -50 ° C + 40 ° C, but most commonly it is mixed at room temperature. It is preferable to perform mixing and subsequent reaction, stirring. After mixing, the mixture is reacted at 40-300 ° C, preferably at 50-200 ° C for 10 minutes to 30 hours.

After the reaction, the reaction mixture is filtered and washed with a solvent such as an aliphatic hydrocarbon or an aromatic hydrocarbon to remove unreacted transition metal compound and polysiloxane, followed by drying.

Thus, the solid product (II) is obtained.

Subsequently, the solid product (II) is reacted with at least two transition metal compounds selected from at least one selected from each group of the halogen-containing transition metal compounds of Group 4a or 5a (Group A).

Examples of the halogen-containing transition metal compound of Group (A) include compounds such as titanium, halides of vanadium, oxyhalides, alkoxy halides, and acetoxy halides, such as titanium tetrachloride, tetrahydrochloride titanium, and trichloromonoisopropoxytitanium. And dichlorodiisopropoxytitanium, monochlorotriisopropoxytitanium, trichloromonobutoxytitanium, dichlorodibutoxytitanium, monochlorotributoxytitanium, vanadium tetrachloride and oxy vanadium tetrachloride. Examples of the halogen-free transition metal compound of Group (B) include alkoxides of titanium and vanadium, for example, tetramethyl ortho titanate (tetramethoxy titanium), ortho titanate tetraethyl (tetraethoxy titanium), and ortho titanate tetra Ortho titanate tetraalkyl (tetraalkoxytitanium), such as isopropyl (tetraisopropoxytitanium), ortho titanate tetran-butyl (tetra-n-butoxytitanium), vanadil triethylate (VO (OC ₂ H ₅ )) ₃ ), vanadil trialcoholates such as vanadil triisopropylate (VO (OCH (CH ₃ ) ₂ ) ₃ ), vanadil tri n, -butylate (VO (OC ₄ H ₉ ) ₃ ), and the like.

As the compound of group (B), polytitanic acid ester can be used in addition to the above. It is represented by the general formula RO-[-Ti (OR) ₂ -O-] nR, m is an integer of at least 2, preferably 2-10, R represents an allyl group, an aryl group or an aralkyl group , Not all R's need to be the same kind of group. The carbon number of R is preferably 1-10, but is not particularly limited. Specific examples include methyl polytitanate, ethyl polytitanate, isopropyl polytitanate, n-propyl polytitanate, n-butyl polytitanate and n-hexyl polytitanate. In general formula, a part of an alkoxy group may be a hydroxyl group. As a compound of (B group), the said one is more preferable than polytitanic acid ester.

At least one kind of transition metal compound may be selected from Group A and at least one kind of transition metal compound from Group B. Therefore, two or more kinds of transition metal compounds may be selected from the same group and used together with those selected from other groups. It is included in the scope of the invention.

Transition metal compounds selected from solid products (II), (A group) and (B group), respectively (hereinafter, these may be referred to as (A group) transition metal compounds and (B group) transition metal compounds, respectively) As a specific method for reacting two or more kinds of transition metal compounds from the above, all are included).

(1) A solid product (II) is added to a mixture of the transition metal compound (Group A) and the transition metal compound (Group B), followed by heating.

(2) After mixing the (A group) transition metal compound with the solid product (II), it is heated by adding the (B group) transition metal compound.

(3) The solid product (II) is heated by reacting the transition metal compound (Group A), followed by the addition of the transition metal compounds (Group B).

And other methods. Any reaction method can be carried out even if a solvent is present or not. The solvent to be used is the same as the solvent mentioned above as a solvent used for the washing | cleaning after reaction or after reaction in the catalyst preparation of this invention.

(A group), (B group) The ratio of the amount of each transition metal compound used (the total amount when using two or more from one group) is (Group B) (B group of the number of transition metal atoms contained in the transition metal compound). ) The ratio of the transition metal compound to it (hereinafter referred to simply as transition metal atomic ratio) is 10 / 1-l / 10, preferably 5 / 1-1 / 5. The ratio of the total weight of the solid product (II) and the transition metal compound is sufficient as 1-l, 000 g with respect to 100 g of the solid product (II). The reaction temperature is 30-500 ° C., preferably 50-300 ° C., and the reaction time is 10 minutes-50 hours, preferably 30 minutes-1 hour. When using a solvent, 0-1,000 ml is enough with respect to 100 g of solid products (II). In this way, the transition metal compound is supported in the solid product (II).

After completion of the reaction, the mixture is filtered by a conventional method, and washed with a solvent such as aliphatic hydrocarbon or aromatic hydrocarbon at room temperature or preferably at 60 ° C. or higher to remove the transition metal compound of the reaction, and dried to obtain a solid product (II). Get)

The solid product (III) is combined with an organoaluminum compound to form a catalyst for polymerization.

As the organoaluminum compound, monoethoxydiethylaluminum, such as trialkylaluminum such as triethylaluminum, triisobutylaluminum and trihexyl aluminum, dialkylaluminum monochloride such as diethylaluminum monochloride, ethylaluminum sesquichloride, and the like And alkoxy alkyl aluminum such as diethoxy monoethyl aluminum.

The catalyst obtained in this way is used for manufacture of the alpha- olefin polymer. Examples of the α-olefins include branched phases such as ethylene, propylene, butene-1, hexene-1, octane-1, dicene-1, other linear monoolefins, and 4-methyl-pentene-1. Diolefins, such as a monoolefin and butadiene, etc., are mentioned, This invention aims not only at the homopolymerization of these but also the copolymerization of said 2 or more types of alpha-olefins which can be copolymerized.

The polymerization reaction is usually carried out in a hydrogen oxide solvent such as hexane, heptane or octane. The polymerization temperature is 30-150 ° C., preferably 60-120 ° C., and the polymerization pressure is performed at atmospheric pressure of −50 kg / cm 2, preferably 5-40 kg / cm 2. At the time of superposition | polymerization, an appropriate amount of hydrogen is added to a superposition | polymerization system, and molecular weight can be adjusted.

The first effect of the present invention is that an olefin polymer having an extremely wide molecular weight distribution can be obtained.

w/

n으로 20-32이고 중합체의 성형시는 유동특성이 양호하고, 성형시의 수지(樹脂)압력이 낮고, 멜트프랙쳐가 일어나지 않기 때문에 성형물의 외관이 양호하고, 성형성(戌形性)이 안정되어 있다. 또, 프로필렌 중합체에서는 입체규칙성(立體規則性)이 높은 것도 특색이다.Especially in ethylene polymers

w /

20-32 n, the flow characteristics are good at the time of molding of the polymer, the resin pressure at the time of molding is low, and no melt fracture occurs, so the appearance of the molding is good, and the moldability is good. It is stable. In addition, the propylene polymer is characterized by high stereoregularity.

The second effect of the present invention is that the polymerization activity is extremely high, and in the case of ethylene polymerization, the polymer yield (in the present invention, the polymer yield means the value according to the following formula, and abbreviated as E _P ) G (polymer) / {solid product (III) (g) x polymerization time (H _r ) x olefin pressure (kg / cm 2)}, thus reaching 1,100. It is possible to eliminate the remaining catalyst, i.e. eliminate the deliming process.

The third effect of the present invention is that the shape of the polymer particles is extremely good. The conformation of the polymer shape can be judged by measuring the volume specific gravity (hereinafter abbreviated as BD) of the polymer powder. Due to the good shape of the polymer particles, the production efficiency per volume of the polymerizer and the hour are large, there is no occurrence of troubles in the pipe transportation of the polymer, and the granulation of the polymer powder is also easy.

The BD obtained by the present invention is 0.35-0.43 in the ethylene polymer and 0.40-0.50 in the propylene polymer, and according to microscopic observation, the particles are spherical or close in shape, and the particle surface is slippery.

Another effect of the present invention is that there is no or very little adhesion of polymer to the polymerizer wall during polymerization, and that long-term stable continuous polymerization can be performed in the same polymerizer. In addition, a new polymerization method that can be used for any of ethylene polymerization and? -Olefin polymerization other than ethylene can be provided. Examples are shown below.

w/

N(

w)는 중량평균 분자량이고,

N은 수(數)평균분자량이다)은 겔퍼어 미에이션 크로마토그래피(gel pemeation chromatography)(Waters사제 GPC-200형)에 의해서 구하였다.In the Examples and Comparative Examples, the cement index (abbreviated as MI) was in accordance with ASTMD-1238 (E), and the melt-flowrate (abbreviated as MFR) was in accordance with ASTMD-1238 (L).

w /

N (

w) is the weight average molecular weight,

N is the number average molecular weight, and was calculated | required by gel pemeation chromatography (type GPC-200 by Waters).

Example 1

(1) Preparation of solid product (II)

58 g of magnesium hydroxide and 90 g of aluminum trichloride (anhydrous) were previously mixed and pulverized in a vibration mill for 5 hours, and then reacted at 150 ° C for 5 hours. Then, it cooled, it grind | pulverized and obtained the solid product (I).

173 g of titanium tetrachloride and 100 g of chained dimethylpolysiloxane (Toshiba silicone oil TSF450-100, viscosity 100 centistokes) were added and mixed in 100 ml of toluene, and then, 100 g of the solid product (I) was added thereto, and stirred at 110 ° C. The reaction was carried out for 2 hours.

After completion of the reaction, filtration is performed first, and the remaining solid product is washed with hexane until no unreacted titanium tetrachloride and unreacted polysiloxane is detected in the filtrate, and dried under reduced pressure to obtain a solid product (II).

Next, 87 g of titanium tetrachloride and 65 g of tetraisopropyl ortho titanate (transition metal atom ratio 2/1) were added and mixed in 400 ml of toluene, and 100 g of the solid product (II) was added thereto and stirred at 3O < 0 > C while stirring. The reaction was time. After completion of the reaction, washing was repeated with hexane until no titanium compound was detected in the filtrate by the usual method, followed by drying under reduced pressure to obtain a solid product (III). The titanium atom in 1 g of solid product (III) was 102 mg.

All operations until the preparation of the solid product (III) must be performed under a nitrogen gas atmosphere containing no moisture. The same is true in the following Examples and Comparative Examples.

(2) polymerization of ethylene

w/

N은 32이고, Ep(중합체 수율)는 1,000이었다.Subsequently, after replacing the nitrogen gas with a volume of 10 L of a polymerizer, 397 mg (2 mmol) of hexane 7 L triisobutyl aluminum and 50 mg of solid product (III) were added thereto, the polymerizer was sealed, and heated to 85 ° C. V) was introduced to 16 kg / cm 2, and polymerization was carried out at 85 ° C. for 1 hour while ethylene was added to maintain the voltage at 35 kg / cm 2 at the gauge pressure. After completion of the reaction, the ethylene polymer slurry was filtered off and dried without drying to obtain 900 g of a white polymer. MI of this polymer is 0.25, BD is 0.40,

w /

N was 32 and Ep (polymer yield) was 1,000.

Comparative Example 1

Instead of the solid product (III), the solid product obtained in Example 1 is used as a final solid product (hereinafter referred to as a final solid product, which is a solid catalyst component used as a catalyst by combining with organic aluminum in Comparative Examples). An ethylene polymer was produced in the same manner as in Example 1 except for the above.

Comparative Example 2

In Example 1, the preparation of the final solid product and the preparation of the ethylene polymer were carried out in the same manner as in Example 1 except that the solid product (I) was used instead of the solid product (II).

Comparative Example 3

In Example 1, the preparation of the final solid product and the preparation of the ethylene polymer were carried out in the same manner as in Example 1, except that the chain polysiloxane was not used to prepare the solid product (II).

[Comparative Example 4]

In Example 1, the final solid product and the ethylene polymer were produced in the same manner as in Example 1, except that titanium tetrachloride was not used in the preparation of the solid product (II).

[Comparative Example 5]

In Example 1, the preparation of the final solid product and the preparation of the ethylene polymer were performed in the same manner as in Example 1, except that ortho tetra titanate tetraisopropyl was not used.

Comparative Example 6

In Example 1, the preparation of the final solid product and the preparation of the ethylene polymer were carried out in the same manner as in Example 1, except that titanium tetrachloride was not used to prepare the solid product (II) from the solid product (II). .

Comparative Example 7

In 100 ml of toluene, 87 g of titanium tetrachloride and 65 g of tetraisopropyl ortho titanate were mixed, reacted at 110 ° C. for 3 hours, cooled, and 500 ml of hexane was added to precipitate a solid product, which was dried by filtration. Got it. An ethylene polymer was prepared in the same manner as in Example 1 except that this solid product was used as the final solid product. At the same time, the polymer yield was significantly lowered, and the polymer shape was poor, and the polymer adhesion to the polymerizer wall was extremely high.

Comparative Example 8

The preparation of the final solid product and the preparation of the ethylene polymer were carried out in the same manner as in Example 1, except that 44 g of the same molar vanadium tetrachloride was used instead of 65 g of tetraisopropyl tetraisopropyl.

Comparative Example 9

Preparation of the final solid product and preparation of the ethylene polymer in the same manner as in Example 1, except that 156 g of the same mole of ort titanate tetra n-butyl was used instead of 87 g of titanium tetrachloride reacted with the solid product (II). Was performed.

Example 2

In 100 ml of toluene, 100 g of solid product (I) obtained in Example 1, 173 g of titanium tetrachloride, and 100 g of dimethyl polysiloxane (50 centimeters of Stokes) were simultaneously mixed at room temperature, and reacted at 110 ° C for 2 hours with stirring. After that, in the same manner as in Example 1 to obtain a solid product (II).

Next, 100 g of solid product (II) and 87 g of titanium tetrachloride were added to 400 ml of toluene, and the mixture was reacted at 110 DEG C for 1 hour while stirring, followed by addition of 65 g of tetraisopropyl ortho titanate (2/1 atomic metal atom ratio). It was reacted again at 110 ° C. for 2 hours. Thereafter, a solid product (II) was obtained in the same manner as in Example 1. Using this solid product (III), it carried out similarly to Example 1, and manufactured the ethylene polymer.

Example 3

80 g of magnesium oxide 75 g aluminum trichloride (anhydrous) was mixed and fractionated for 24 hours in a bowl mill, and then reacted at 50 ° C. for 50 hours to obtain a solid product (I).

In 150 ml of hexane, 100 g of the solid product (I) and 100 g of the chain dimethylpolysiloxane (1,000 centimeters of viscosity) were added and mixed. Then, 130 g of titanium tetrachloride was added and reacted at 60 ° C. for 9 hours to give a solid product ( II).

Next, 100 g of the above solid product and 29 g of tetramethyl ortho titanate were added to 500 ml of xylene, and then 95 g of titanium tetrachloride (transition metal atom ratio 3/1) was added and reacted at 140 ° C. for 3 hours to give a solid product. (III) was obtained.

Using this solid product (III), an ethylene polymer was produced in the same manner as in Example 1.

Example 4

40 g of aluminum magnesium oxide (MgA1 ₂ O ₄ ) and 85 g of iron trichloride (anhydrous) were mixed and ground in a vibrating mill for 7 hours, and then reacted at 100 ml for 10 hours to obtain a solid product (I).

100 g of the solid product (I) and 100 g of titanium tetrachloride were added and mixed at room temperature in 100 ° C. of benzene, and immediately, 100 g of chain methylethylpolysiloxane (viscosity 100 centistokes) was added thereto, and reacted at 78 ° C. for 7 hours. Solid product (II) was obtained.

Next, 100 g of the solid product (II) and 114 g of titanium tetrachloride were added to 200 ml of benzene, and the reaction was carried out at 78 ° C. for 5 hours, and then 58 g of tetrabutyl ortho titanate (35/1 atomic metal atom ratio) was added again. It reacted at 78 degreeC for 5 hours, and obtained solid product (III).

Using this solid product, it carried out similarly to Example 1, and manufactured the ethylene polymer.

Example 5

80 g of magnesium carbonate and 80 g of aluminum chloride (anhydrous) were mixed and pulverized in a bowl mill for 10 hours, and then reacted at 200 ° C for 1,5 hours to obtain a solid product (I).

500 g of octamethyl cyclotetra siloxane (2 centimeters Stokes) and 190 g of titanium tetrachloride were mixed, the solid product (I) was added thereto, and the mixture was reacted at 200 ° C. for 30 minutes to obtain a solid product (II).

Next, in 250 ml of toluene, 127 g of titanium tetrachloride and 81 g of vanadil triisopropylate [VO (OCH (CH ₃ ) ₂ ) ₃ ] (transition metal atom ratio 2/1) were mixed, and the solid was added thereto. 100 g of product (II) was added, and the mixture was reacted at 110 ° C for 4 hours to obtain a solid product (III).

Using this solid product (III), an ethylene polymer was produced in the same manner as in Example 1.

Example 6

65 g of magnesium chloride (MgC1 ₂ 6H ₂ O) and 80 g of aluminum chloride (anhydrous) are mixed and fractionated in a vibration mill for 2 hours,

It was made to react at 150 degreeC for 5 hours, and solid product (I) was obtained.

100 g of the solid product (I), 100 g of the chain methylphenyl polysiloxane (200 cm Stokes) and 150 g of titanium tetrachloride were simultaneously mixed with 100 ml of toluene at room temperature, and then reacted at 100 ° C. for 6 hours to obtain a solid product (II). .

Next, 89 g of vanadium tetrachloride and 65 g of tetraisopropyl tetraisopropyl (transition metal atom ratio 2/1) were mixed in 300 ml of trichlorobenzene, and 100 g of the solid product (II) was added thereto, and the mixture was stirred at 200 ° C for 1 hour. Reaction gave solid product (III).

Using this solid product (III), an ethylene polymer was produced in the same manner as in Example 1.

Example 7

110 g of magnesia cement (MgC1 ₂ 3MgO 4 H ₂ O) and 95 g of aluminum chloride (anhydrous) were mixed and pulverized in a vibration mill for 3 hours, and then reacted at 130 ° C for 4 hours to obtain a solid product (I).

In 300 ml of toluene, 100 g of the solid product (I) and 50 g of titanium tetrachloride were mixed at room temperature, 100 g of methyl hydride polysiloxane (viscosity 100 centistokes) was added thereto, and the mixture was reacted at 110 ° C for 1 hour to give a solid product. (II) was obtained.

Using this solid product (II), in the same manner as in Example 2, preparation of the fourth solid product (III) and preparation of the ethylene polymer were performed.

Example 8

80 g of hydromagnesite ( ₃ MgCO ₃ · Mg (OH) ₂ · 3H ₂ O) and 120 g of aluminum chloride (anhydrous) were mixed and pulverized in a vibration mill for 10 hours, and then reacted at 300 ° C. for 30 minutes to obtain a solid product (I). Got.

In 200 ml of xylene, 100 g of the solid product (I), 100 g of dimethylpolysiloxane (100 cm Stokes), and 190 g of titanium tetrachloride were simultaneously mixed at room temperature, and reacted at 130 ° C. for 1 hour to give solid product (II). Got.

Next, in 400 ml of xylene, 100 g of the solid product (II), 95 g of titanium tetrachloride, and 57 g of tetraethyl ortho titanate (2/1 atomic metal atom ratio) were simultaneously mixed at room temperature, followed by reaction at 130 ° C. for 1 hour. To give a solid product (III).

Using this solid product (III), an ethylene polymer was produced in the same manner as in Example 1.

Example 9

In Example 1, after obtaining the solid product (II), 100 g of the solid product (II) was dissolved in 400 ml of toluene, 32 g of isopropyl ortho titanate, 39 g of tetra n-butyl ortho titanate, and 87 g of titanium tetrachloride (transition metal source). After mixing with Zn 2/1), the solid product (III) was prepared and the ethylene polymer was produced in the same manner as in Example 1.

Example 10

100 g of the solid product (II) obtained in Example 1 was the same as in Example 1 except that 53.4 g of trichloromonoisopropoxy titanium and 101 g of vanadyl triethylate (1/2 of a transition metal atom ratio) were reacted. In this way, preparation of the solid product (III) and preparation of the ethylene polymer were carried out.

Example 11

100 g of the solid product (II) obtained in Example 1 was subjected to the same procedure as in Example 1, except that 53 g of dibutoxy titanium and 172 g of vanadyl tri n-butylate were reacted with dichloro. Thus, solid product (III) was prepared and ethylene polymer was produced.

Example 12

Ethylene containing 8% (volume%) of propylene so as to introduce hydrogen up to 9 kg / cm 2 gauge pressure using the solid product (III) obtained in Example 1 and maintain the voltage at 35 kg / cm 2 at the gauge pressure Except for adding, the ethylene-propylene copolymer was prepared in the same manner as in Example 1.

Example 13

The solid product (III) obtained in Example 1 was used to induce hydrogen up to 10 kg / cm 2 (gauge pressure) and to maintain the voltage at 35 kg / cm 2 (gauge pressure) butene-1 10% (capacity 1%) An ethylene-butene copolymer was prepared in the same manner as in Example 1 except that ethylene was added.

The result of 1-9 is put together in the 1st table | surface of the above-mentioned implementation and comparison, and is shown in a 1st table | surface.

Example 14

Using the solid product (III) obtained in Example 1, propylene was polymerized. Into a 5 L styrenic polymerizer, 3.5 L of hexane, 210 mg of diethyl aluminum chloride, and 50 mg of solid product (III) were added, and a hydrogen partial pressure of 1 kg / cm 2 (gauge pressure) and a propylene partial pressure of 10 kg / Cm 2 pressure), the reaction was carried out at 70 ° C for 4 hours.

은 9, 아이소택틱인덱스(중합체를 비등하는n-헥탄중(98℃)에서 4시간 추출하고 남은 추출찌꺼기의 추출전의 중합체 중량에 대한 비율)은 0.92이고, 중합체) 수량(收量)은 고체생성물(Ⅲ) 1당(當) 5,900g이였다.MFR of the obtained polymer is 4.2, BD is 0,47,

Silver 9, isotactic index (ratio of polymer residue before extraction of extracted residues left after extraction for 4 hours in n-hexane boiling polymer (98 DEG C)) was 0.92, and polymer) yield was solid It was 5,900 g per product (III).

Example 15

A butene polymer was produced in the same manner as in Example 12 except that 500 g of butene-1 was used instead of propylene. The polymer yield was 900 g per solid product (III).

In any of the above Examples 1-15, adhesion of the polymer to the polymerizer wall was not seen.

Example 16

(1) Preparation of solid product (III)

In 100 ml of toluene, 173 g of titanium tetrachloride and 100 g of chained dimethylpolysiloxane (Toray Silicone SH-200, followed by viscosity 100 centistokes) were added and mixed, and the solid product obtained in the same manner as in Example 1 was obtained. 100 g was added and reacted at 110 degreeC for 2 hours, stirring.

After completion of the reaction, filtration was carried out according to a conventional method, and the remaining solid product was washed with hexane until no unreacted titanium tetrachloride and unreacted polysiloxane was detected in the filtrate, and the solid product (II) was dried under reduced pressure. Got it.

Next, 87 g of titanium tetrachloride and 46.4 g of polyisopropyl isopropyl (5-molecular polymer) were added and mixed in 400 ml of toluene (transition metal atom ratio 2/1), and 100 g of solid product (II) was added thereto, followed by stirring It was made to react at 110 degreeC for 3 hours. After completion of the reaction, the mixture was warmed up to 80 ° C. and filtered, and the remaining solid product was washed with toluene heated to 80 ° C. until no titanium compound was detected in the filtrate, and dried under reduced pressure to obtain 150 g of solid product (III). The titanium atom in 1 g of solid product (III) was 95 mg. All operations up to production of the solid product (III) must be performed in a nitrogen gas atmosphere containing no water.

(2) polymerization of ethylene

The polymerization of ethylene was carried out in the same manner as in Example 1, except that the solid product (III) was used after being replaced. After completion of the reaction, methanol was added to terminate the polymerization, and the ethylene polymer slurry was filtered off and dried without deliming to yield 810 g of a white polymer.

MI 0.23 and BD of this polymer were 0.39, MW / MN was 30, and the polymer yield (EP) was 900.

Comparative Example 10

An ethylene polymer was prepared in the same manner as in Example 16 except that the solid product (II) obtained in Example 16 was used as the final solid product instead of the solid product (III).

Comparative Example 11

In Example 16, the preparation of the final solid product and the preparation of the ethylene polymer were carried out in the same manner as in Example 16, except that the solid product (I) was used instead of the solid product (II).

Comparative Example 12

In Example 16, the preparation of the final solid product and the preparation of the ethylene polymer were carried out in the same manner as in Example 16, except that no polysiloxane was used to prepare the solid product (II).

Comparative Example 13

In Example 16, the preparation of the final solid product was carried out in the same manner as in Example 16, except that titanium tetrachloride was not used in the preparation of the solid product (II), and the ethylene polymer was prepared.

Comparative Example 14

In Example 16, the preparation of the final solid product and the preparation of the ethylene polymer were carried out in the same manner as in Example 16, except that isopropyl polytitanate was not used.

Comparative Example 15

In Example 16, preparation of the final solid product and preparation of the ethylene polymer were carried out in the same manner as in Example 16, except that titanium tetrachloride was not used when preparing the solid product (III) from the solid product (II). It was done.

[Comparative Example 16]

The preparation of the final solid product and the ethylene polymer in the same manner as in Example 16 except that 40 g of vanadium oxytrichloride in an amount equivalent to the transition metal atom ratio thereof was used instead of isopropyl polytitanate. Was prepared.

[Comparative Example 17]

In Example 16, the same procedure as in Example 16 was carried out except that 126 g of polytitanate n-butyl (two-molecular polymer) was used in an amount equivalent to the transition metal atom ratio instead of titanium tetrachloride reacted with the solid product (II). The preparation of the final solid product and preparation of the ethylenic polymer were carried out.

[Comparative Example 18]

In 100 ml of toluene, 87 g of titanium tetrachloride and 46.4 g of polytitanic isopropyl (5-molecular polymer) were mixed, reacted at 110 ° C. for 2 hours, and then cooled to room temperature, followed by hexane 400 If it is left to add ㎖, the solid product precipitates. Filtration, washing with hexane phosphorus and drying gave a solid product. Using this as the final solid product, an ethylene polymer was prepared in the same manner as in Example 16.

Comparative Example 19

An ethylene polymer was produced in the same manner as in Example 16, except that 25 mg of the solid product (II) obtained in Example 16 and 76 mg of the solid product obtained in Comparative Example 18 were combined and used as the final solid product.

[Comparative Example 20]

In Example 16, preparation of the final solid product and preparation of the ethylene polymer were carried out in the same manner as in Example 16, except that 78 g of silicon tetrachloride (SiC1 ₄ ) was used instead of titanium tetrachloride reacted with the solid product (II). It was done.

Comparative Example 21

In Comparative Example 20, except that 61 g of aluminum trichloride (anhydrous) was used instead of silicon tetrachloride, the preparation of the final solid product and the production of ethylene polymer were carried out in the same manner as in Comparative 20.

Example 17

In Example 16, the reaction of the solid product (II), titanium tetrachloride, and isopropyl polytitanate was carried out in 100 ml of toluene, and then the reaction solution was cooled to room temperature and left to stand by addition of 400 ml of hexane. , Solid product was filtered out. Washed with hexane and dried to obtain 180 g of solid product (III). Using this solid product (III), an ethylene polymer was produced in the same manner as in Example 16.

Example 18

75 g of magnesium oxide and 80 g of aluminum chloride (anhydrous) were mixed and pulverized in a bowl mill for 24 hours, and then reacted at 100 ° C for 10 hours to obtain a solid product (I).

In 100 ml of benzene, 100 g of solid product (I) and 100 g of chain methylphenyl polysiloxane (500 centistokes of viscosity) were added and mixed. Then, 150 g of titanium tetrachloride was added and reacted at 80 ° C. for 7 hours to give a solid product (II). )

Next, 100 g of solid product (II) and 69 g of n-butyl polytitanate (two-molecular polymer) were added to 400 ml of xylene, and then 96 g of vanadium tetrachloride was added (transition metal atomic ratio 3/1), and 130 ° C. The mixture was reacted for 3 hours, and then, in the same manner as in Example 16, preparation of the solid product (III) and preparation of the ethylene polymer were performed.

Example 19

Hi deureu magnesite and iron trichloride _{(3MgCO 3 · Mg (OH)} 2 · 3H 2 O) 65g ( anhydrous)

After 70 g of the mixture was ground and mixed in a vibration mill for 10 hours, the mixture was reacted at 300 ° C for 1 hour to obtain a solid product (I).

In 200 ml of xylene, 100 g of solid product (I), 50 g of titanium tetrachloride and 100 g of hydrogenated methyl polysiloxane (50 centistokes of viscosity) were added thereto, and the mixture was reacted at 130 ° C for 1 hour to obtain a solid product (II).

Next, 100 g of solid product (II) and 86 g of vanadium oxychloride were added and mixed in 300 ml of toluene, and then 41 g of ethyl polytitanate (6-molecular polymer) was added (transition metal atomic ratio 2/1) to 120 ° C. The mixture was reacted for 4 hours, and then, in the same manner as in Example 16, preparation of the solid product (III) and preparation of the ethylene polymer were performed.

Example 20

The solid product (III) obtained in Example 16 was used to introduce hydrogen 릍 up to 9 kg / cm 2 (gauge pressure) and contain 8% (volume%) of propylene to maintain the voltage at 35 kg / cm 2 at the gauge pressure. Except adding ethylene, it carried out similarly to Example 16, and manufactured the ethylene propylene copolymer. Propylene content in the copolymer was 3.1%.

Example 21

Using the solid product (III) obtained in Example 16, hydrogen was introduced up to 10 kg / cm 2 (gauge pressure), and 10% (volume%) of butene-1 was maintained at 65 kg / cm 2 (gauge pressure). ) An ethylene-butene copolymer was prepared in the same manner as in Example 16 except that ethylene was added. The content of butene-1 in the copolymer was 5.2%.

The result of Example 16-21 and Comparative Example 10-21 mentioned above is put together, and is shown in a 2nd table.

Example 22

Propylene was polymerized using the solid product (III) obtained in Example 16. Into a 5 L polymerizer, 3.5 L of hexane, 228 mg of triethyl aluminum and 50 mg of solid product (III) were added, and the hydrogen partial pressure of 1 kg / cm 2 (gauge pressure) and the propylene partial pressure of 10 kg / cm 2 (gauge pressure) were adjusted to 70 ° C. The reaction was carried out for 4 hours. Obtained polymer MFR was 4.5, BD was 0.45, isotactic index was 0.91, and the polymer yield was 5,800 g / g of solid product (III).

은 9.2었다.Polymer

Was 9.2.

은 작고, 이것을고체생성물(Ⅲ)으로하는 것에 의해서 분자량 분포는 비약적으로 넓게 된다는 것을 알 수 있다. 비교예 2-4,11-13에 의하여, 본발명에 있어서 (A군) 및 (B군) 천이금속화합물을 반응시키는 대상의 고체생성물이 특정한 것(고체생성물(Ⅱ))이 아닌 경우에는, 중합체 수율이 현저하게 낮은 것이라고 하는 것을 알 수 있다.According to Comparative Examples 1 and 10, the solid product (II) as it is

It is small and it turns out that molecular weight distribution becomes remarkably wide by making this as solid product (III). According to Comparative Examples 2-4 and 11-13, in the present invention, when the solid product to be reacted with the (Group A) and (B Group) transition metal compounds is not a specific one (solid product (II)), It can be seen that the polymer yield is remarkably low.

Comparative Examples 5, 6, 8, 9, and 14-17 show that both (A group) and (B group) are required as the transition metal compound to be reacted with the solid product (II).

According to Comparative Examples 7,18 and 19, the transition metal cobalt (Group A) and Group (B) in the present invention exhibited an effect by reacting the solid product (II) with (Group A) It can be seen that the effect of the present invention is not caused by the mixing of the reaction product of the transition metal compound and the group B transition metal compound.

In Comparative Examples 20 and 21, the reaction of the solid product (II) with the (B group) transition metal compound is a compound containing halogen, but at the same time, it does not have the effect of the present invention unless it also contains the transition metal. .

Claims (1)

A method for producing an olefin polymer by homopolymerizing or copolymerizing α-urepin using a catalyst obtained by combining a solid product containing a transition metal atom of Group 4a or 5a of the periodic table with an organoaluminum compound. In addition, the presence of polysiloxane in the solid product (I) obtained by reacting a trivalent metal halide with a hydroxide, oxide or carbonate of a divalent metal, or a hydrate of a divalent metal compound as the solid product. Transition metal compound of Group 4a or Group 5a under the following reaction, and the transition metal compound of Group 4a or Group 5a containing (A) halogen again to the solid product (II) thus obtained and Group (B) Obtained by reacting at least two transition metal compounds selected from each group of the transition metal compounds of Group 4a or Group 5a containing no halogen. The process for producing an olefin polymer, characterized in that the use of solid product (III).