JPS63122711A - Catalyst for polymerization of olefins - Google Patents

Abstract

PURPOSE:To provide the titled catalyst capable of giving highly stereoregular polyolefin without any deashing operation, comprising a piperizine derivative, organoaluminum compound and a specific solid component prepared from magnesium compound, aluminum compound, titanium compound, liquid hydrocarbon and electron donor. CONSTITUTION:The objective polymerization catalyst can be obtained by formulation of (A) a solid catalytic component (B) a piperizine derivative of formula (R<1>-R<4> are each H, alkyl, etc.) and (C) an organo-aluminum compound. The solid catalytic component A can be made as follows: MgCl2 and Al2O3 are ground together to prepare a substance. This substance, <=2pts.wt. based on 1pt.wt. of said substance of a tetraalkoxytitanium, an aliphatic hydrocarbon liquid at -30-+50 deg.C, and an aliphatic alcohol are mixed to form a homogeneous solution. This solution is then dripped on TiCl4 kept at <=0 deg.C followed by addition of a phthalic diester at >=80 deg.C, then reaction at >=100 deg.C. The resulting solid is separated, being allowed to react with TiCl4.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is capable of producing highly stereoregular polymers with high activity and uniform shape when subjected to the polymerization of olefins. This relates to high-performance catalysts. More specifically, the present invention provides a catalyst for polymerizing olefins comprising a special solid catalyst component (a specific piperidine derivative (II) and an organoaluminum compound), as will be detailed later. be.

[Prior art]

Recently, instead of the conventionally well-known titanium trichloride catalyst component as a solid catalyst component in catalysts for polymerizing olefins such as propylene, a new type of catalyst component has been developed in which the active component titanium is supported on magnesium chloride together with an electron donor. Many things have been developed and proposed.

Among these, the earliest developed one was a complex of an organic monocarboxylic acid ester as an electron donor and titanium tetrachloride co-pulverized with magnesia chloride, or an organic monocarboxylic acid ester as an electron donor. There is a product obtained by co-pulverizing carboxylic acid nysterte with magnesium chloride and treating it with titanium tetrachloride.

However, these cannot be said to have satisfactory characteristics for use on an industrial scale, and there are methods that have several times the characteristics, such as those that use jetoxymagnesium instead of magnesium chloride, and those that use jetoxymagnesium as an electron donor. Various methods have been proposed in which special compounds are used, or methods of combining the above-mentioned substances, contact means, etc. are modified.

For example, in JP-A-54-94590, a catalyst component is prepared using magnesium dihalide as a starting material,
A method is disclosed in which organic aluminum compounds, organic carboxylic acid esters, compounds having an M-0-R group, etc. are used in combination for the polymerization of olefins, and JP-A-57-63310 discloses that organic aluminum compounds, organic carboxylic acid esters, compounds having an M-0-R group, etc. are used in combination for the polymerization of olefins. There is a method in which a catalyst component is prepared by combining various esters of , active magnesium chloride, and a titanium compound, and then propylene is polymerized using a compound having an 81-0 bond or a 5i-N bond and an organoaluminum compound. Disclosed.

[Problem that the invention seeks to solve]

In the prior art, chlorine contained in magnesium chloride, which is the main carrier material, has a negative effect on the produced polymer, similar to the halogen element in titanium halides.
It has the disadvantage of having negative effects.

In addition, when polymerizing olefins, particularly stereoregular polymerization of propylene, 1-butene, etc., is carried out industrially using the catalyst component having magnesium chloride as a carrier in combination with an organoaluminum compound, the polymerization reaction is carried out. In this case, it is essential to use an organic senocarboxylic acid ester as an electron donor. However, in this case, it is necessary to use an extremely large amount of organic monocarboxylic acid ester, and as a result, there is a problem in that the resulting polymer has a characteristic ester odor.

Furthermore, in so-called highly active supported catalysts, such as catalysts using catalyst components with magnesium chloride as a carrier, although the activity is high at the initial stage of polymerization, deactivation over time causes problems in process operation, and block copolymerization It was practically impossible to use it when the polymerization time was made longer.

To improve this point, the above-mentioned Japanese Patent Application Laid-Open No. 54-9459
No. 0 has been proposed, but as is clear from the description in the same publication, in this case it is necessary to use an organic carboxylic acid ester both during catalyst preparation and during polymerization. Generally, the amount of organic carboxylic acid ester contained in the catalyst is such that the problem of odor of the produced polymer during treatment with a titanium halide or washing with an organic solvent can be ignored.

However, as mentioned above, the amount of organic acid ester used during polymerization is extremely large compared to the amount contained in the catalyst, and when polymerization is carried out in liquid or gaseous monomers, most of the At present, all of these substances are contained in the produced polymer, and therefore, it can be said that the problem of odor in the produced polymer cannot be solved unless an organic acid ester is used during polymerization. Furthermore, as can be seen from the examples, the method disclosed in the same publication requires very complicated table operations, and the catalyst obtained is practically sufficient in terms of performance and sustainability of activity. The reality is that this cannot be said.

[Disclosure of the invention]

The present inventors conducted intensive research to solve the various problems in the prior art as described above, and the present invention provides a high-performance catalyst capable of producing a polymer having a high degree of stereoregularity. succeeded in doing so.

That is, the present invention provides a catalyst for polymerizing olefins characterized by comprising the solid catalyst component (II) below, the piperidine derivative (II) below, and (or more) an organoaluminum compound.

(II) A substance (a) obtained by pulverizing magnesium chloride and aluminum oxide, tetraalkoxytitanium (b) in an amount of 2 parts by weight or less per 1 part by weight of the substance (a),
A homogeneous solution is prepared using an aliphatic hydrocarbon (c) that is a liquid at -30°C to 50°C and an aliphatic alcohol-tv (d) that is a liquid at -30°C to 50°C; was added dropwise to titanium 94 chloride (e) maintained at a temperature below 0°C, and then the resulting solution was heated to 80°C or above with stirring to form a diester of phthalic acid tv (r
), separate the solid product obtained by reacting at a temperature of 100° C. or higher, and react it with titanium tetrachloride; (II) General formula (in the formula R1 , HR1R3, gloss is hydrogen or an alkyl group which may have a substituent, at least one of R1 and R is an alkyl group, and at least one of 2 and gloss is an alkyl group. The present invention provides a catalyst for polymerizing olefins comprising a di- or tetra-substituted piperidine derivative represented by (2) an organoaluminum compound.

The catalyst for polymerizing olefins of the present invention will be explained in more detail below.

First, the solid catalyst component (II) will be explained.

To obtain the substance obtained by pulverizing magnesium chloride and aluminum oxide (hereinafter simply referred to as Gl substance) in (a) above, commercially available magnesium chloride and aluminum oxide are ball-milled in an inert atmosphere, and then shaken. Grinding is carried out using a mill or the like at an ambient temperature of usually 5 minutes or more, preferably 10 minutes or more and 50° C. or less.

The aluminum oxide used in the production of the substance (a) above can be appropriately selected from commercially available products. Note that the usage ratio of magnesium chloride and aluminum oxide is arbitrary as long as it does not adversely affect the performance of the resulting catalyst component, and is not particularly limited.
It is used in the range of L1 to 2t.

As the tetraalkoxytitanium (hereinafter simply referred to as (b) substance) of the above gloss, an alkoxy group having 1 to 10 carbon atoms is used, and one having 3 or 4 carbon atoms is particularly preferable. used.

These tetraalkoxytitaniums can be used alone or as a mixture of two or more. O: l) The amount of the substance to be used is 2 parts by weight or less per 1 part by weight of the (a) substance. For example, usually, the amount of (LOI ~ 1 ton) of the (a) substance per 1fK is Used within the range of.

The above (c) aliphatic hydrocarbon (hereinafter referred to as monoK (c) substance) and the above (d) aliphatic alcohol (hereinafter referred to as monoK)
(d) Substances) are all liquid at -30°C to 50°C.

(c) Preferable examples of the substance include aliphatic hydrocarbons having 5 to 12 carbon atoms, such as pentane, hexane, heptane,
Examples include octane, nonane, decane, and dodecane, and preferred examples of the substance (d) include 2 to 1 carbon atoms.
0 aliphatic alcohols such as ethanol, propatool, phthanol, pentanol, hexanol, etc.

The substance (c) and the substance ((II) are used in appropriate amounts within the range that allows preparation of a homogeneous solution.

Note that the concept of solution used in the present invention also includes a suspended state.

Thus, (de) substance, (c) substance, and (
i) A homogeneous solution of the substance is prepared and the resulting solution is added dropwise to titanium tetrachloride (e) kept below 0° C. without forming a precipitate. At this time, titanium tetrachloride (
e) is 1- or more preferably 5 with respect to (a) substance 1f.
Used at a ratio of 4 or more.

After the dropwise addition is completed, the temperature is raised while stirring to precipitate a solid substance,
Further, the diester of phthalic acid (f) is added at 80° C. or higher while stirring.

In this case, in order to obtain particles with a good outer particle shape, it is preferable to increase the temperature at a rate of 0.S.degree. C./min or less.

Diesters of phthalic acid (hereinafter simply referred to as (f) substance) mentioned above (f) include diethyl phthalate, diethyl phthalate, diisopropyl A/7 thalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate V-),
Examples include cyamyl phthalate (V-), diisoamyl phthalate, ethylbutyl phthalate F, ethyl isobutyl phthalate, and ethylpropyl phthalate.

The above substance (f) is used in a ratio of 0.1- or more, preferably 0.2- or more, to (a) substance 1f.

(f) After addition of the substance, at a temperature of 100°C or higher
The reaction is allowed to proceed for at least 50 minutes, preferably at least 50 minutes.

The solid product obtained is then separated.

Separation of the solid product is normally carried out by means used to separate solid materials from liquids, such as decantation or filtration.

Next, a solid catalyst component (II) is obtained by reacting this solid product with titanium tetrachloride.

The contact temperature at this time is usually 0°C or higher and 130°C or lower. The contact time is at least 10 minutes, preferably at least 30 minutes. The amount of titanium tetrachloride used is at least 1, preferably at least 5, per ton of the solid product.

The obtained solid catalyst component (II) may be washed with an organic solvent such as nihebutane, if necessary, and may be reacted repeatedly with titanium tetrachloride. In this reaction with titanium tetrachloride, titanium tetrachloride is preferably used after being diluted with an aromatic hydrocarbon such as toluene.

In any case, the solid catalyst component (II) K may be subjected to the above reaction with titanium tetrachloride or washing with an organic solvent such as n-hebutane repeatedly as necessary.

All of these embodiments are included in one embodiment of the practice of the present invention.

The series of operations related to the preparation of the solid catalyst component (II) in the present invention is preferably carried out in the absence of oxygen, moisture, and the like.

The solid catalyst component (II) prepared as described above comprises the piperidine derivative (II) and the solid catalyst component (2).
The catalyst for polymerizing olefins according to the present invention is composed of the organoaluminum compound of (II1)
Specific examples of di- or tetra-substituted piperidine derivatives include 2.6-diituprobilbiperidine, 2.6-sibutylpiperidine, 2.2.6.6-teF-ramethylpiperidine, Examples include 2,2,46-tetophethylpiveridine, among which 2,2,46-tetophethylpiveridine is preferred.

Examples of the organoaluminum compound in (2) above include triple-kyl aluminum, sia μ-kyl aluminum halide, alkyl aluminum civalide, and mixtures thereof. Among them, triple-kyl aluminum is preferable, and triethyl aluminum is more preferable. and triisobutylaluminum are particularly preferred.

Is the organoaluminum compound mentioned above the titanium in the solid catalyst component? The piperidine derivative is used in an amount of 1 to 1,000 mos per atom, and the piperidine derivative is used in a ratio of 7 to the organoaluminum compound of 1 or less, preferably in a range of 5 to (LOO).

The polymerization reaction using the polymerization catalyst according to the present invention can be carried out in the presence or absence of an organic solvent,
Further, the olefin monomer used can be in either gas or liquid form. Polymerization temperature is 200
℃ or less, preferably 100℃ or less, and the polymerization pressure is 10
0kg/c, I・G or less preferably so ky/j・
G or less.

Olefins to be homopolymerized or copolymerized using the olefin polymerization catalyst according to the present invention include ethylene, propylene, 1-butene, and the like.

〔Effect of the invention〕

When the catalyst for olefin polymerization according to the present invention is used to polymerize olefins, it exhibits an unprecedentedly high activity, so that the amount of catalyst residue present in the resulting polymer is extremely reduced. The effect of chlorine can be reduced to such an extent that no demineralization step is required for the product.

Chlorine remaining in the produced polymer causes corrosion of equipment used in processes such as granulation and molding, as well as deterioration and yellowing of the produced polymer itself. The results obtained will greatly benefit the technical field.

Further, according to the catalyst of the present invention, the major problem of ester odor adhesion to the produced polymer can be solved by not adding an organic carboxylic acid ester during polymerization.

Furthermore, conventionally, there has been a common drawback in so-called highly active supported catalysts that the activity per unit time of the catalyst decreases significantly as the polymerization progresses, but in the catalyst according to the present invention, Since the decrease in activity over time of polymerization is extremely small compared to conventionally known catalysts, it is also useful in cases where the polymerization time is much longer, such as in copolymerization, and is useful in bulk polymerization and It can also be widely used in gas phase polymerization.

Moreover, according to the catalyst according to the present invention, a polymer having a uniform particle size and a high degree of stereoregularity can be obtained.

Furthermore, in the production of industrial olefin polymers, it is common to coexist hydrogen during polymerization from the viewpoint of MI control, but conventional catalysts have poor activity and stereoregularity in the coexistence of hydrogen. It had the disadvantage of being significantly reduced. However, when olefins are polymerized in the presence of hydrogen using the catalyst according to the present invention, the activity and stereoregularity do not decrease even when the MI of the resulting polymer is extremely high. Such an effect was strongly desired by those skilled in the art.

〔Example〕

The present invention will be explained in more detail below using examples.

Example 1 (II) (a) Preparation of the substance Magnesium chloride 30? and aluminum oxide 10F in a nitrogen gas atmosphere with a total capacity of 5 filled with 25-φ stainless steel poles. OL vibration mill bottle) K charged, vibration frequency 1450V.

Pulverization was carried out for 20 hours at a shaking width of 5 m.

(2) Preparation of solid catalyst component Pulverized product obtained in (II) above 5. Of, tetofuptoxytitanium Table 5-, decane 251R1 and 2-ethylhexyl alcohol 25tdtlEX, into a 200-volume round bottom flask well purged with gas, 130'
After preparing a homogeneous solution by raising the temperature to T: 20 °C in a round bottom flask with a capacity of 500 fnt equipped with a stirrer.
The mixture was added dropwise to 200°C to avoid precipitation, and the temperature was raised at a rate of 13°C/min under stirring to precipitate a solid product. The mixture was kept at that temperature for 2 hours with continuous stirring. After that, the supernatant was removed, and to the obtained solid product was added 1 fresh Ti (450 m1 and 50 ml toluene).
The reaction was carried out at 15°C for 2 hours.

After the reaction was completed, the product was washed 10 times with 100° C. of n-heptane to obtain a solid catalyst component.

At this time, the titanium content in the solid catalyst component was measured and found to be 1.50 weight y.

(3) Polymerization internal volume of propylene2. Using an OL autoclave with a stirring device, after completely replacing the autoclave with nitrogen gas, triethylaluminum 20011F, 2. λ~6-tetofumethylviveridine 25■ and the solid catalyst component! Loaded LO Misaki.

Thereafter, 1.8 t of hydrogen gas and 1.4 t of liquefied propylene were charged, and a polymerization reaction was carried out at 70° C. for 1 hour. After the polymerization reaction is completed, the resulting polymer is dried under reduced pressure at 80° C., and the resulting residue is kept as a prisoner. Further, this product is extracted with boiling n-hebutane for 6 hours to obtain a polymer insoluble in n-hebutane, and the amount of this product is set to 0).

The polymerization activity (c) of the solid catalyst component used is expressed by the following formula.

Further, the yield (CD) of the total crystalline polymer is expressed by the following formula.

Further, the amount of residual chlorine in the produced polymer is expressed as (6), the MI of the produced polymer is expressed as (g), and the bulk specific gravity is expressed as (G), and the obtained results are shown in Table 1.

Example 2 An experiment was conducted in the same manner as in Example 1 except that the polymerization time was 30 minutes. □The results obtained are shown in Table 1.

Example 3 An experiment was carried out in the same manner as in Example 1, except that the same amount of zoprobyl phthalate as rK of digtylphthalate was used. Note that the titanium content in the solid catalyst component at this time was 1.
It was 66% by weight.

During polymerization, an experiment was conducted in the same manner as in Example 1.

The results obtained are as shown in Table 1.

Example 4 A solid catalyst component was prepared in the same manner as in Example 1, except that heptane was used instead of decane when preparing a homogeneous solution.

In addition, the titanium content in the solid catalyst component at this time was 1.7
It was 0% by weight.

For the first case, conduct the experiment in the same manner as in Example 7. , It was a woman. The results obtained are as shown in Table 1.

Table 1

[Brief explanation of the drawing]

FIG. 1 is a schematic drawing to help understand the present invention.

Claims (1)

[Claims] 1) (I) Substance (a) obtained by pulverizing magnesium chloride and aluminum oxide, tetraalkoxytitanium (2 parts by weight or less) per 1 part by weight of substance (a). b) preparing a homogeneous solution with an aliphatic hydrocarbon (c) that is liquid at -30°C to 50°C and an aliphatic alcohol (d) that is liquid at -30°C to 50°C; The solution was added dropwise to titanium tetrachloride (e) maintained at 0°C or below, and then the temperature of the resulting solution was raised with stirring, and diester of phthalic acid (f) was added at 80°C or above. A solid catalyst component obtained by separating the solid product obtained by reacting at a temperature of ℃ or higher and reacting it with titanium tetrachloride; (II) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R^1, R^2, R^3, and R^4 are hydrogen or an alkyl group that may have a substituent, and at least R^1 and R^2 One is an alkyl group, and at least one of R^3 and R^4 is an alkyl group.) and (III) an organoaluminum compound. Catalyst for polymerizing olefins.