JPH0196201A - Catalyst for olefin polymerization - Google Patents

Abstract

PURPOSE:To provide a high-performance catalyst acting in high activity when applied to olefin polymerization, capable of obtaining highly stereoregular polymers with well-ordered shape, consisting of a specific solid catalytic component, epoxy-p-menthane compound and organoaluminum compound. CONSTITUTION:The objective catalyst consisting of (A) a solid catalytic component, (B) an epoxy-p-menthane compound, and (C) an organoaluminum compound. The component A can be prepared by the following processes; using a magnesium halide, <=2pts.wt. per pt.wt. of said magnesium halide, of a tetraalkoxytitanium, and aliphatic hydrocarbon and aliphatic alcohol liquid at -30-50 deg.C, a homogeneous solution is prepared followed by dripping said solution into TiCl4 at <=0 deg.C and rise of temperature while stirring to separate a solid matter out and furthermore adding a phthalic diester at >=80 deg.C while stirring to produce a solid product. This product is then separated, being brought into contact with TiCl4 in the presence of an aromatic hydrocarbon or aromatic halogenated hydrocarbon each liquid at normal temperature.

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, which comprises a special solid catalyst component (1), an epoxy paramenthane compound (n), and an organoaluminum compound (2), as will be detailed later. It comes out.

[Prior art and its problems] In place of the conventionally well-known titanium trichloride catalyst component as a solid catalyst component in catalysts for polymerizing olefins such as propylene t-humidity, this new type of catalyst component is an active component. Many materials have been developed and proposed in which titanium is supported on magnesium chloride together with an electron donor.

Among these, the earliest developed was a complex of an organic monocarboxylic acid ester as an electron donor and titanium tetrachloride co-pulverized with magnesium chloride, or a complex of an organic monocarboxylic acid ester as an electron donor and titanium tetrachloride, or There is a possibility that the co-milled product of acid nysterte and magnesium chloride should be treated with titanium tetrachloride.

However, when these are used in combination with organoaluminum compounds for industrial polymerization of olefins, especially stereoregular polymerization of propylene, 1-butene, etc., organic monocarboxylic acids are used as electron donors during the polymerization reaction. It is essential to use an ester, and in this case, it is necessary to damage the organic monocarboxylic acid ester and use it in a large amount, resulting in the problem of imparting a characteristic ester odor to the resulting polymer.

Furthermore, although these catalysts have high activity at the initial stage of polymerization, their deactivation over time poses a problem in process operation, and when the polymerization time is increased, such as in block copolymerization, it is practically impossible to use them. was impossible.

To improve this point, JP-A No. 54-94590 discloses that a catalyst component is prepared using magnesium dihalide as a starting material, and organic aluminum compounds, organic carboxylic acid esters, compounds having an M-0-R group, etc. A method is disclosed in which the combination is used for the polymerization of olefins, 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. In general, the organic carboxylic acid ester contained in the catalyst is treated with a titanium halide or washed with an organic solvent, so that the concentration of the organic carboxylic acid ester is reduced to such a level that the odor of the produced polymer can be ignored. However, as mentioned above, the amount of organic carboxylic 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, almost all of it is produced. At present, tjb is contained in the polymer, and therefore, it can be said that the problem of odor in the produced polymer cannot be solved unless an organic carboxylic acid ester is used during polymerization. Furthermore, as can be seen from the examples, the method disclosed in the same publication requires very complicated operations, and the catalyst obtained is not sufficient for practical use 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 comprises the following solid catalyst component (1), the following epoxy paramenthane compound (II), and the following (
[[This invention provides a catalyst for polymerizing olefins, which is characterized by being made of an organoaluminum compound of D.

(1) Magnesium halide (a), tetraalkoxytitanium (b) in an amount of 2 parts by weight or less per 1 part by weight of the magnesium halide (a), -30°C to 5°C
Aliphatic hydrocarbons rc) which are liquid at 0°C and -
A homogeneous solution is prepared using an aliphatic alcohol (d) which is liquid at 30°C to 50°C, and then the solution is kept at below 0°C and converted into titanium 9tetrachloride (θ).
The solution obtained is added dropwise without precipitation, then the temperature of the resulting solution is raised with stirring to precipitate a solid substance, and the diester (f) of phthalic acid is added at 80° C. or higher with further stirring. (II) Epoxy Paramenthane Compound and Tsukuda) A catalyst for polymerizing olefins comprising an organoaluminum compound is provided.

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

First, the solid catalyst component (1) will be explained. Magnesium rogenide of (a) above (hereinafter simply referred to as (a)
It is called substance. ) include magnesium chloride, magnesium bromide, magnesium iodide, etc. Among them, magnesium chloride is preferred.

Tetraalkoxytitanium of (b) above (hereinafter simply referred to as (b)
As the alkoxy group, those having 1 to 10 carbon atoms are used, and those having 3 or 4 carbon atoms are particularly preferably used.

One type of tetraalkoxy titanium can be used alone, or two or more types can be used as a mixture. (b) The amount of the substance used is 2 parts by weight or less per 1 part by weight of the (a) substance, for example, usually (a) 1 part by weight of the substance. 0)
The material used is in the range of 101 to 1t.

The aliphatic hydrocarbon (c) (hereinafter simply referred to as (c) substance) and the aliphatic alcohol (a) (hereinafter simply referred to as (c))
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, gropanol, butanol, pentanol, hexanol, etc.

The substance (c) and the substance (1) are used in appropriate amounts as long as a homogeneous solution can be prepared.

Thus, a homogeneous solution of (a) substance, (b) substance, (C) substance, and (cl) substance is prepared, and the resulting solution is heated with titanium tetrachloride (e ) without forming a precipitate. In this case, titanium tetrachloride (e) is preferably used in a ratio of 1d or more, preferably U5d5d, to 1f of the substance (a).

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

At this time, in order to obtain particles with good particle shape, it is preferable to increase the temperature at a rate of G, 5° C./min or less.

Examples of the phthalic acid diesters (hereinafter simply referred to as (f) substance) in (1) include dimethyl phthalate, diethyl phthalate, diimpropylphthalate, and dipropylphthalate V-
), dibutyl 7-thalate, cyinobutyl phthalate, cyamyl phthalate, diisoamyl phthalate, ethyl butyl phthalate, ethyl isobutyl phthalate and ethyl propyl phthalate.

The above substance (f) is (a) substance 1? It is preferably used in a ratio of α1- or more, and α2- or more.

(f) After addition of the substance, the mixture is further maintained at a temperature of 80° C. or higher for 10 minutes or more, preferably 30 minutes or more.

The solid product obtained is then separated.

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

Next, this solid product is mixed with aromatic hydrocarbons, which are liquid at room temperature, if
The solid catalyst component (1) is obtained by bringing c into contact with titanium tetrachloride in the presence of an aromatic halogenated hydrocarbon (2) (hereinafter simply referred to as (ω substance)).

The contact temperature at this time is usually 0°C or more and 130°C or less. 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 1 of the above solid product, and the amount of (g) substance is ad per 1 of titanium tetrachloride.
d~20-1 preferably 0.2-10-1. The substance (g) used in this case is preferably toluene, xylene, O-dichlorobenzene, or the like.

The obtained solid catalyst component (1) may be washed with an organic solvent such as n-hebutane or toluene if necessary, and may be repeatedly treated with titanium tetrachloride or titanium tetrachloride in the presence of an ω substance. May be brought into contact.

All of these aspects are included in one aspect of implementing the present invention.

In the present invention, the series of operations related to the preparation of the solid catalyst component in (1) above are preferably carried out in the absence of oxygen, moisture, and the like.

The solid catalyst component (1) prepared as above is combined with the epoxy paramenthane compound (11) and the organic aluminum compound (110) to constitute the catalyst for polymerizing olefins according to the present invention. However, the epoxy paramenthane compound of (11) above is 1.4
-Epoxyparamenthane and (1,8-epoxyparamenthane) are preferred, but it is also possible to use these with a substituent such as an alkyl group or halogen.

The organoaluminum compounds of the above (IID) include trialkylaluminum, dialkylaluminum halide, alkylaluminum dino1lide, alkylaluminum moschino\lide, and mixtures thereof.
Among them, trialkylaluminum is preferred, and triethylaluminum and triisobutylaluminum are particularly preferred.

The organoaluminum compound (l) is used in an amount of 1 to 1000 mol per titanium atom in the solid catalyst component, and the epoxy paramenthane compound is used in a molar ratio of 1 or less to the organoaluminum compound, preferably f'i [Lo
It is used in the range of 05 to 1.0.

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 used in either gas or liquid state. Polymerization temperature is 200
℃ or less, preferably 100℃ or less), and the polymerization pressure is 10
0kl? /α2・G or less is preferable! 50 to 9/α2・
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. Moreover, since the residual chlorine is extremely volatile, the influence of chlorine can be reduced to such an extent that the product does not require any deashing step at all.

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 be of great benefit to the field of technology.

Further, according to the catalyst of the present invention, by not adding an organic carboxylic acid ester during polymerization, it is possible to solve the major problem of ester odor imparting to the resulting polymer.

Furthermore, conventionally, there has been a common drawback in so-called high-activity supported catalysts in that the activity of the catalyst per unit time decreases significantly as the polymerization progresses, but in the catalyst according to the present invention, Since the activity decreases with the passage of polymerization time is extremely small compared to conventionally known catalysts, it is useful in cases where the polymerization time is longer, such as in copolymerization, and at higher polymerization pressures. Since the increase in activity is large when it is used, it can be widely used in bulk polymerization and gas phase polymerization, which have recently been attracting attention.

Moreover, according to the catalyst according to the present invention, a polymer having a well-shaped structure 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 controlling the M process, but using conventional magnesium chloride as a carrier and organic carboxylic acid ester. The catalyst used had the disadvantage that its activity and stereoregularity were significantly reduced in the presence of hydrogen. However, when olefin polymerization is carried out in the presence of hydrogen using the catalyst according to the present invention,
The activity and stereoregularity are not reduced even when the M engineering of the resulting polymer is extremely high. Such an effect was strongly desired by those skilled in the art. In addition, in the industrial production of polyolefins, the bulk specific gravity of the produced polymer is a very big problem in terms of the capacity of polymerization equipment, the capacity of post-treatment processes, etc., but the catalyst according to the present invention also has this problem. , has extremely excellent properties.

Furthermore, the polymer produced using the catalyst according to the present invention has a narrow particle size distribution and is nearly spherical.

In addition, it does not produce fine powder polymers that are undesirable in the polyolefin manufacturing process, and is suitable for gas phase polymerization, which has been attracting attention recently.
l? ! ! In addition to facilitating the so-called post-polymerization treatment steps such as the above, it also has various effects such as the ability to omit the granulation step due to its excellent particle shape.

〔Example〕

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

Example 1 (1) Adjustment of solid catalyst component Magnesium chloride 4.8? , tetrabutoxy titanium & rho, decane 25wLt and 2-ethylhexyl alcohol 25- with a capacity of 200d fully replaced with nitrogen gas.
The temperature was raised to 130°C to prepare a homogeneous solution, and then the Tic solution was placed in a 9-volume 500° round-bottomed flask equipped with a stirrer at 20°C. /4200- in order not to form a precipitate, and the temperature was raised at a rate of 12°C/min under stirring to precipitate a solid product. At 110°C, dibutyl phthalate 5-5- was added and the mixture was heated at that temperature. Stirring was continued for 2 hours in the dark.

After that, the supernatant liquid was removed, and to the obtained solid product, 50- toluene and 50- T1C1a were newly added.
The reaction was carried out at 5°C for 2 hours. After the reaction is completed, the product t-40
The solid catalyst component was obtained by washing with 200 d of n-hebutane at 10° C. for 10 times.

At this time, when the titanium content in the solid catalyst component was measured, it was found to be 1.76% by weight.

(2) Using an autoclave equipped with a stirrer and having an internal volume of 201 ml of propylene polymerization, the autoclave was completely replaced with nitrogen gas, and then 200 y of triethylaluminum, 70 ~ 1,8-epoxy paramenthane, and 5.011 g of the solid catalyst component were prepared. I loaded it. after that,
Charged 1.8t of hydrogen gas and 4t of liquefied propylene, and
The polymerization reaction was carried out at 0°C for 1 hour. After the polymerization reaction is completed, the produced polymer is dried under reduced pressure at 80°C, and the obtained product is designated as (4). Also, add this to boiling n-hebutane for 6 hours.
After time extraction, a polymer insoluble in n-hebutane is obtained, which is referred to as "it'eω)".

The polymerization activity (C) based on the nine solids and catalyst components used is expressed by the following formula.

Further, the yield Φ of the total crystalline polymer is expressed by the following formula.

Furthermore, the amount of residual chlorine in the produced polymer is expressed as (■), the Mlt (Mlt) of the produced polymer, and the bulk specific gravity is expressed as (G), and the obtained results are shown in Table 1.

The average particle diameter of the obtained polymer was about 20-0 μm and it had a transparent appearance.

Implementation v7rU2 An experiment was conducted in the same manner as in Example 1 except that the polymerization time was t-30 minutes. The results obtained are as shown in Table 1.

The obtained polymer had an average particle size of about 170 μm and was transparent.

Example 3 An experiment was carried out in the same manner as in Example 1 except that the polymerization reaction was carried out in the following manner.

Contents completely replaced with nitrogen gas $2. Charge n-hebutane 700- to an OL autoclave with a stirring device,
Triethyl aluminum 30 while maintaining nitrogen gas atmosphere
0ag, 100Mg of 1.8-epoxy paramenthane, then 15.0Mg of the solid catalyst component prepared by the method of Example 1.
q was charged.

Thereafter, hydrogen gas was charged at 120° C., the temperature was raised to 70° C., and propylene gas was introduced while maintaining a pressure of 6 J/cm”·G to carry out a polymerization reaction for 1 hour. After the polymerization reaction was completed, The obtained subhedral polymer was taken from house to house, heated to 80°C, and dried under reduced pressure.Meanwhile, the amount of polymer dissolved in the polymerization solvent after condensing the p liquid is ω), and the amount of solid polymer is ( 1).

Further, the obtained solid polymer was extracted with boiling n-hebutane for 6 hours to obtain a polymer insoluble in n-hebutane, and this cost was designated as (J).

The polymerization activity (8)) per solid catalyst component is expressed by the following formula.

Further, the yield of the crystalline polymer (CL) k is expressed by the following formula, and the yield of the total crystalline polymer (C) is determined by the formula below.

Further, residual chlorine 2 (N) in the produced polymer, M error (0) of the produced polymer, and bulk specific gravity are expressed as ψ). The results obtained are shown in Table 2.

The average particle size of the obtained polymer was approximately 110 μm, and it had a transparent appearance.

Example 4 An experiment was carried out in the same manner as in Example 3, except that the polymerization time was changed to t-2 hours. The results obtained are summarized in Table 2.

The average particle size of the obtained polymer was approximately 130 μm, and it had a transparent appearance.

Run 8ilIJ5 Run F except that the same amount of dipropylphthalate was used instead of dibutyl phthalate! The experiment was conducted in the same manner as AU1. Note that the titanium content in the solid catalyst component at this time was 1.92% 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.

Furthermore, the average particle diameter of the obtained polymer was about 190 μm, and it had a transparent appearance.

Table 1 Table 2

[Brief explanation of the drawing]

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

Claims (1)

[Claims] 1) (I) Magnesium halide (a), tetraalkoxytitanium (b) in an amount of 2 parts by weight or less per 1 part by weight of the magnesium halide (a), -30°C to 50°C A homogeneous solution is prepared using an aliphatic hydrocarbon (c) that is liquid at °C and an aliphatic alcohol (d) that is liquid at -30 to 50 °C, and then the solution is maintained at below 0 °C. The resulting solution was then added dropwise to titanium tetrachloride (e) without forming a precipitate, and the temperature of the resulting solution was then raised with stirring to precipitate a solid substance, and the phthalic acid The solid product obtained by adding the diester (f) is separated and contacted with titanium tetrachloride in the presence of an aromatic hydrocarbon or an aromatic halogenated hydrocarbon (g) which is liquid at room temperature. A solid catalyst component obtained by: (II) an epoxy paramenthane compound and (III) an organoaluminum compound.