JPH02202502A - Polymerization catalyst for olefins - Google Patents

Abstract

PURPOSE:To provide the subject catalyst containing epoxy p-menthane, an organic Al compound and a solid component composed of a Mg halide, esters. Ti alkoxides, alcohols, TiCI4, etc., and giving a highly stereoregular polymer having uniform shape. CONSTITUTION:The objective polymerization catalyst is produced by compounding (A) a solid catalyst component produced by crushing (i) a magnesium halide and (ii) a phthalic acid diester, adding (iii) a tetraalkoxytitanium, (iv) an aliphatic alcohol and (v) a phthalic acid diester (which may be different from or same as the component ii) successively to the above crushed product in the presence of (vi) an aliphatic hydrocarbon at >=100 deg.C and treating the product further with (vii) titanium tetrachloride, (B) an epoxy p-menthane compound and (C) an organic aluminum compound.

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 (I), an epoxy paramenthane compound (II), and an organoaluminum compound, as will be detailed later. be.

[Conventional technology]

Recently, instead of the well-known titanium trichloride catalyst component as a solid catalyst component in the polymerization of 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 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-milling carboxylic acid nysterte with magnesium chloride and treating it with titanium tetrachloride.

[Challenges remaining in conventional technology]

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. Since it is essential to use an ester, and in this case it is necessary to use an extremely large amount of an organic monocarboxylic acid ester, there is a problem in that the produced polymer has a characteristic ester odor.

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 longer, such as in block copolymerization, it is virtually impossible to use them. It was impossible.

In order to improve this point, JP-A-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 acid ester during catalyst preparation and during polymerization. There is. Generally, the amount of organic carboxylic acid ester contained in the catalyst is such that the problem of odor of the produced polymer can be ignored even after treatment with a titanium halide or washing with an organic solvent. 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 a liquid or gaseous mass, almost all of it is At present, it is contained in the produced polymer, and therefore, it can be said that the problem of odor in the produced polymer cannot be solved as long as 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 resulting catalyst is not sufficient for practical use in terms of performance and sustainability of activity. The reality is that this cannot be said.

[Means to solve the problem]

The inventors of the present invention have conducted intensive research to solve the various problems in the prior art as described above, and have found that the present invention provides a high-performance catalyst capable of producing a polymer having a high degree of stereoregularity. It was very successful.

That is, the present invention comprises the following m solid catalyst component and the following r
The epoxy paramenthane compound of f[) and the following (In
The present invention provides a catalyst for polymerizing olefins, characterized by comprising an organoaluminum compound of the following.

(1) After pulverizing magnesium halide (a) and phthalic acid diester (b), the resulting product is heated at 100°C or less in the presence of an aliphatic hydrocarbon (c), and tetrafalkoxytitanium (d), Aliphatic alcohol/L/(θ) and phthalic acid diester/I/(e) ((b) and (f) may be the same or different) are added sequentially and treated respectively. A solid catalyst component obtained by adding titanium tetrachloride (g) to the obtained product and further treating it; This is what we provide.

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

First, the solid catalyst component m will be explained. Said (
Examples of the magnesium halide in a) (hereinafter simply referred to as substance (a)) include magnesium chloride, magnesium bromide, and magnesium iodide, with magnesium chloride being preferred.

The above ('b) phthalic acid diester (hereinafter referred to as single K (bl
Examples of substances) include dimethyl phthalate, diethyl phthalate, diisopropylphthalate, dipropylphthalate V-), dibutyl phthalate, diisobutyl phthalate, diamiμbuta V-), diisoamyl phthalate,
Examples include ethyl butyl phthalate, ethyl isobutyl phthalate, and ethyl propyl phthalate.

(b) The amount of the substance used is usually in the range of 0.1 to 10 f in total per 1 ton of (at substance).

The aliphatic hydrocarbon of the above (c) (hereinafter simply referred to as the (c) substance) and the aliphatic alcohol of the above fe) (hereinafter simply referred to as the (c) substance)
θ) substances) are all liquid at -50°C to 50°C.

(c) Preferable examples of the substance include aliphatic hydrocarbons having 5 to 12 carbon atoms, such as pentane, hexane, butane,
Examples include octane, nonane, decane, dodecane, and isomers thereof, and preferred examples of te) substances include aliphatic alcohols having 2 to 10 carbon atoms, such as ethanol 1-propano-μ, butanol, pentano- , hexano-, octatool, and isomers thereof.

tetophykoxytitanium of the above cd) (hereinafter simply referred to as (d)
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 or more of these Tetofa μCoquintitanium compounds can be used. The amount of the (a) substance used is usually in the range of a total of r1.1 to 10F per (a) substance 1f.

The phthalic acid diester lv (hereinafter simply referred to as (1) substance) of (f) can be appropriately selected from those exemplified above.

The above substance (f) is preferably α1- or more, preferably α2-1. Used in low proportions.

Titanium tetrachloride (g) used in the present invention is (a)
It is used at a ratio of 1 to 12 of the substance, preferably 51 or more.

The contact temperature at this time is usually 0°C or higher and 130°C or lower. The contact time is 10 minutes or more, preferably 50 minutes or more.

The obtained solid catalyst component (I) may be washed with an organic solvent such as n-hebutane or toluene, if necessary, or may be repeatedly treated with titanium tetrachloride (g).

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

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

The solid catalyst component (1) prepared as above is combined with the silicon compound (II) and the organoaluminum compound (function) to constitute the catalyst for polymerizing olefins according to the present invention. As the compound (n) above, 1,4-epoxyparamenthane or 1,8-epoxyparamenthane is preferable, but it is also possible to use these with a substituent such as alkyl iv or halogen. .

Examples of the organoaluminiums, compounds, and compounds of the above (III) include trialkylaluminum, sialkyl aluminum hafide, alkylaluminum cibaphyte, arylaminium sesquihafide, and mixtures thereof, among which, Trialkylaluminum is preferred, and triethyl aluminum and trialkylaluminum are particularly preferred.

Is the organoaluminum compound of the above function the titanium in the solid catalyst component? The epoxy paramenthane compound is used in an amount of 1 to 1000 moles per atom, and the 7y ratio of the epoxy paramenthane compound to the organoaluminum compound is 1 or less, preferably α005 to 1.
Used in the range 0.

The polymerization reaction using the polymerization catalyst according to the present invention can be carried out in the presence of an organic solvent or in the absence of L.
Further, the olefin polymer used can be used in either a gas or liquid state. Polymerization temperature is 200
℃ or less, preferably 100℃ or less, and the polymerization pressure is 10
0kl? /am”・G or less, preferably 50 Yu/-2・G
It is as follows.

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

[Functions and effects 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. In addition, since the amount of residual chlorine is extremely small, the influence of chlorine can be reduced to such an extent that no deashing process 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. This will also bring great benefits 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 adhering to the produced polymer.

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, The decrease in activity with the passage of polymerization time is extremely small compared to conventionally known catalysts, so it is useful when polymerization times are longer, such as in copolymerization, and higher polymerization pressures are used. Since the increase in activity is large in this case, it can be widely used in bar 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, it does not produce powdery polymers that are undesirable in the polyolefin manufacturing process, and is suitable for gas phase polymerization, which has been attracting attention recently, and because it still has poor fluidity, it can be used after so-called polymerization such as pumping or centrifugation. Various effects can be achieved, such as facilitating the treatment process and omitting the granulation process, which produces excellent particle shapes.

〔Example〕

EXAMPLES Below, the present invention will be explained in more detail with reference to Examples.

Example 1 (1) Preparation of solid catalyst component Magnesium chloride 30F and normal to normal μ phthalate)
Zl- was placed in a 1.0 t capacity vibrating mill pot filled with 25 φ stainless steel poles in a nitrogen gas atmosphere, and the vibration frequency was 1430 v, p, m, and the swing width was 55 m.
The mixture was crushed for 17 hours.

In a round bottom flask with a capacity of 50Nd equipped with a stirrer, 10r of the above pulverized product and 75% of n-decane were added under a nitrogen gas atmosphere.
- and tetofuptoxytitanium 10- and 130
The temperature was raised to .degree. C. and the treatment was carried out for 1 hour while stirring. Next, a solution of 25 mg of n-hebutane and 2-ethylhexyl alcohol &8- was added dropwise to the mixture over a period of 30 minutes, and the mixture was reacted for 1 hour while maintaining a temperature of 130 tons. After that, it was cooled to 7Q'C, and further n-hebutane 25-
and n-butyl phthalate) mixed solution of 1.0 d was added to 30
It was added dropwise over a period of 1 minute, heated to 90°C, and treated for 1 hour. The obtained product was washed five times with 200-helbutane, and after sowing, TiC475- was added and reacted at 110° C. for 3 hours. After the reaction was completed, the mixture was washed 10 times with 200-g of hebutane to obtain a solid catalyst component.

At this time, the titanium content in the solid catalyst component was measured and found to be 5.06 by weight.

(2) Polymerization of propylene Using an O-F crepe with a stirring device and an internal volume of 2.0 t, after completely replacing it with nitrogen gas, 200 II g of triethyl aluminum, 70 g of 1.8-epoxy paramenthane
The cape and the solid catalyst components tA and Oq were charged. After that, 1.8 tons of hydrogen gas.

1.4 tons of liquefied propylene was charged, and a polymerization reaction was carried out at 70°C for 1 hour. After the polymerization reaction is completed, the produced polymer is
Dry under reduced pressure at 0°C, and let the amount of the obtained product be (A).

In addition, this product was extracted with boiling n-hebutane for 6 hours and n-
A polymer insoluble in hebutane is obtained, and the amount of this polymer is defined as (■).

The polymerization activity (0) per solid catalyst component used is expressed by the following formula.

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

CB) ω"I= -X 1 0 0 (@ (A) Furthermore, the amount of residual chlorine in the produced polymer is expressed as (to)), the M process of the produced polymer is expressed as (IP), and the obtained results are It is 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 dipropylphthalate was used instead of dibutyl phthalate. Incidentally, the titanium content in the solid catalyst component at this time was 5.19% by weight. Example 1 for polymerization
An experiment was conducted in the same manner. The results obtained are shown in Table 1.

Part 1 table

[Brief explanation of the drawing]

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

Claims (1)

[Claims] 1) (I) After pulverizing magnesium halide (a) and phthalic acid diester (b), the obtained product is heated at 100°C or higher in the presence of an aliphatic hydrocarbon (c). Tetraalkoxytitanium (d), aliphatic alcohol (e) and phthalic acid diester (f) ((b) and (f) may be the same or different) are added sequentially and treated respectively. , a solid catalyst component obtained by adding titanium tetrachloride (g) to the obtained product and further processing; an olefin characterized by comprising (II) an epoxy paramenthane compound and (III) an organoaluminum compound Catalyst for polymerization.