JPH0258509A - Catalyst for polymerizing olefins - Google Patents

Abstract

PURPOSE:To obtain the subject catalyst capable of providing a highly stereoregular polymer having a uniform shape by blending a component consisting of Mg, an alkyl halide, I2, Ti compound, alcohols, phthalic acid chloride and TiCl4 with an Si compound and organoaluminum compound. CONSTITUTION:The objective catalyst for polymerization obtained by blending (A) a solid catalyst component prepared by pulverizing a product obtained by reacting metallic Mg powder with an alkyl monohalide in an amount of >=2 times based on the powder in the presence of iodine and a tetraalkoxytitanium, successively adding the tetraalkoxytitanium, aliphatic alcohol and phthalic acid dichloride in the presence of an aliphatic hydrocarbon at >=70 deg.C, respectively carrying out treatment, adding titanium tetrachloride to the resultant product and further treating the product with (B) an Si compound expressed by the formula (R is alkyl, vinyl, aryl, etc.; R' is alkyl; 0<=m<4) and (C) an organoaluminum 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 consisting of a special solid catalyst component (1), a specific silicon compound (U), and an organoaluminum compound, as will be detailed later. It is.

[Conventional technology and its issues]

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 and titanium tetrachloride as an electron donor, which was co-pulverized with magnesium chloride, or an organic monocarboxylic acid ester as an electron donor. There is a co-pulverized product of carboxylic acid ester and magnesium chloride 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. ester? In addition, in this case, it is necessary to use an extremely large amount of organic monocarboxylic acid ester, which poses 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 causes problems in the operation of the proscene, and when the polymerization time is increased in block copolymerization, etc., the f′L is substantially reduced. It was impossible to use.

This point? As an improvement, in JP-A-54-94590, a catalyst component is prepared using magnesium dihalide as a starting material, and an olefin is prepared by combining an organoaluminum compound, an organic carboxylic acid ester, a compound having an M-0-R group, etc. However, 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 particular, the amount of organic carboxylic acid ester used during polymerization is extremely large, and when polymerization is carried out in liquid or gaseous monomers, almost all of it is presently contained in the resulting polymer. Therefore, it can be said that the problem of the odor of the produced polymer cannot be solved only by using organic carboxylic acid esters. Furthermore, as can be seen from the series of implementations, the method disclosed in the same publication requires complicated operations, and the resulting catalyst is not practical in terms of performance and sustainability of activity. The reality is that it cannot be said to be sufficient.

[d! Problem (+- Means for Solving) The present inventors conducted intensive research in order to solve the various problems in the above-mentioned conventional techniques, and found that the present invention provides a highly advanced three-dimensional structure. VC succeeded in providing a high-performance catalyst that can yield polymers with regularity.

That is, the present invention provides a catalyst for polymerizing olefins, which is characterized by comprising the solid catalyst component (1) below, the silicon compound <n) below, and the organoaluminium compound below (Ill).

(1) Substance (a) obtained by reacting metallic magnesium powder with at least twice the mole of alkyl monohalide in the presence of iodine and tetraalkoxytitanium (b) are crushed, and the resulting product is mixed with fat. Tetraalkoxytitanium (1)), aliphatic alcohol (d) and phthalic dichloride (e) at 70°C or above in the presence of group hydrocarbon (Q)
Solid catalyst component obtained by adding titanium tetrachloride (f) to the obtained product and further processing; (It) General formula SiRm(oR')4-m (Component R is an alkyl group, cycloalkyl group, vinyl group, or aryl group, and R' is an alkyl group. When R is an alkyl group, the alkyl group HR' may be the same. mdo≦ The present invention provides a catalyst for polymerizing olefins comprising a silicon compound represented by m (4) and an organoaluminum compound (4).

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.

A substance (hereinafter simply referred to as (a) substance) obtained by reacting the metal magnesium powder of (a) and an alkyl monohalide in the presence of iodine (hereinafter simply referred to as substance (a)) tl-obtained Kr! , a commercially available metallic magnesium powder and an alkyl monologonide are reacted in the absence of an organic solvent and in the presence of iodine. It is necessary to use mol or more. The reaction temperature and reaction time are arbitrary as long as the above reaction proceeds sufficiently, and are not particularly limited, but the reaction is usually carried out at 20°C or higher for 10 minutes or more, preferably at 40°C or higher for 30 minutes or more. It will be done. This reaction is a Grignard type reaction, and when the R spectrum of the substance (a) obtained by the reaction is measured, absorption of alkyl groups is observed.

The alkyl monochlorides used in the production of the substance (a) are preferably chlorides of aliphatic hydrocarbons that are liquid at room temperature, such as n-globyl chloride, inglobyl chloride, Ω - Bunal chloride, inbutyl chloride, pentyl chloride, hexyl chloride and octyl chloride.

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 or two or more types of tetraalkoxytitanium can be used. The amount of the (b) substance used is usually in the range of a total of α1 to 10y based on 12 of the (a) substances.

The aliphatic hydrocarbon (c) (hereinafter simply referred to as (c) substance) and the aliphatic alcohol (d) (hereinafter simply referred to as (c))
, i) substance] are all liquid at -30°C to 50°C.

Preferred examples of the substance (C) include aliphatic hydrocarbons having 5 to 12 carbon atoms, such as pentane, hexane, heptane,
Examples include octane, heptane, decane, dodecane, and isomers thereof, and preferred examples of the substance (d) include aliphatic alcohols having 2 to 10 carbon atoms, such as ethanol, glopanol, butanol, pentanol, hexanol, Octatool and their isomers are available.

The above (e) phthalic acid dichloride (hereinafter simply referred to as (e) substance) is used in a ratio of α1m or more to (a) substance 1f.

Titanium tetrachloride (f) used in the present invention is (a)
It is used in a ratio of 12 or more, preferably ri,5'1 or more to 11 of the substances.

The contact temperature at this time is usually 0°C or higher and 150°C or lower. The contact time r1 is at least 110 minutes, preferably at least 30 minutes.

The obtained solid catalyst component (1) may be washed with an organic solvent such as n-hebutane or toluene, if necessary, or may be repeatedly treated with titanium tetrachloride (f).

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

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

The solid solvent component (1) prepared as described above contains the silicon compound (II) and the till)
The silicon compound of (11) is combined with an organoaluminum compound of (11) to constitute the catalyst for polymerizing olefins according to the present invention. Examples of alkoxysilanes include tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, phenyltriynepropoxysilane, diphenyldimethoxysilane, and diphenyljethoxysilane. , ethyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, ethyltriinepropoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, divinyljethoxysilane, divinyldimethoxysilane, etc. Can be done.

The organic aluminum compound of (m) includes trialkylaluminum, dialkylaluminum halide,
Alkylaluminum dino 1lide, alkylaluminum sesquino 1lide, and mixtures thereof can be mentioned, among which trialkylaluminum is preferred, and triethylaluminum and triisobutylaluminum are particularly preferred.

The organoaluminum compound of Q[l] is used in an amount of 1 to 1000 mol per 2 atoms of titanium in the solid catalyst component, and the silicon compound has a molar ratio of 1 or less to the organoaluminum compound, preferably α005 to Used in range.

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 single filter 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
It is less than 0 Yu/α2·G, preferably less than 50 Yu/α2·G.

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

[Operation and Effects of the Invention] When the catalyst for polymerizing olefins according to the present invention is used to polymerize olefins, it exhibits a high activity that could not be expected in the past. Furthermore, since the amount of residual chlorine is extremely small, the shadow 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. The results obtained will be of great benefit to the field of technology.

Further, according to the catalyst of the present invention, the major problem of ester odor attached to the produced polymer can also be solved by not using an organic carboxylic acid ester.

Furthermore, conventionally, there was a common drawback in so-called high-activity supported catalysts in that the activity per unit time of the catalyst decreased to a large I viscosity as the polymerization progressed, but in the catalyst according to the present invention, , the decrease in activity over time of polymerization is extremely small compared to conventionally known catalysts, making it useful for longer polymerization times such as copolymerization, and employing higher polymerization pressures. Since the increase in activity is large in this case, 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, hydrogen is used during polymerization. Although it is common to coexist with hydrogen from the viewpoint of M engineering control, etc., the activity and stereoregularity of conventional catalysts using magnesium chloride as a carrier and organic carboxylic acid esters decrease significantly in the coexistence of hydrogen. It had the following drawback. 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 fine powder polymers that are undesirable in the polyolefin manufacturing process, and is suitable for gas phase polymerization, which has been attracting attention recently.It also has good fluidity, so it is suitable for so-called post-polymerization treatments such as pumping and centrifugation. In addition to making the process easier, since the particle shape is crushed, the granulation process can be omitted, and various other effects can be achieved.

〔Example〕

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

Example I+11 (11(a) Preparation of Materials Using a 2.0 t capacity round bottom flask equipped with a stirrer,
After sufficiently replacing this with nitrogen gas, gold 4 magnesium powder 301, iodine 1.0? and 1.21 f of n-butyl chloride were charged, and the reaction was allowed to proceed for 5 hours at the boiling point of n-butyl chloride. After the reaction was completed, the supernatant solution was removed, and the product was washed three times with 500-D-butyl chloride and dried under reduced pressure to obtain a powdery substance.

(2) Preparation of solid catalyst component In a 25 m
The total volume of φ stainless steel balls filled with light is gtoz.
placed in a vibrating mill pot with a vibration frequency of 1430 v, p,
The cod was crushed for 17 hours using a shaking width of 55 mm.

In a round bottom flask with a capacity of 500 g Lt equipped with a stirrer, 10 t of the above pulverized product and 77 n-deca were added under a nitrogen gas atmosphere.
0 mA and 12 tnt of tetrabutoxytitano were charged, the temperature was raised to 125° C., and treatment was performed for 1 hour with stirring. Next, a solution of 25 ml of n-hebutane and 7.1 d of 2-ethylhexyl alcohol was added to the mixture over a period of 30 minutes, and the mixture was reacted for 1 hour while maintaining the temperature at 125°C. After that, it was cooled to 80°C, and further n-hegetane 2
A mixed solution of 5m and phthalic acid dichloride t7- was added dropwise over a period of 60 minutes, and the temperature was raised to 90°C and treated for 1 hour. The obtained product was washed five times with 200-helbutane, and then TiC4,75d was added and reacted at 115°C for 3 hours. After the reaction was completed, the product was washed 10 times with 200 d of hebutane to obtain a solid catalyst component.

At this time, when the titanium content in the solid catalyst component was measured, it was 589! It was t%.

(3) Polymerization internal volume of propylene2. An Ot autoclave equipped with a stirring device was used, and after the autoclave was completely replaced with nitrogen gas, 200 q of triethylaluminum, 50 ql of diphenyldimethoxysilane, and 5.0 q of the solid catalyst component were charged. After that, 1.4t of hydrogen gas and 1.4t of liquefied propylene were charged, and
The polymerization reaction was carried out at 0°C for 1 hour. After the polymerization reaction is completed, the resulting polymer is dried under reduced pressure at 80°C, and the amount of product obtained is ? (A). Also, this one is Wonaten Ω-6 with hebutane.
After time extraction, a polymer insoluble in n-hebutane was obtained, the amount of which was given as 03).

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

The MI of the molded combination is expressed as CF), and the obtained results are expressed as
Shown in the table.

Example 2 An experiment was carried out in the same manner as in Example 1 except that the polymerization time was changed from 11 to 30 minutes.The results obtained are shown in Table 1.

Example 3 An actual experiment was carried out in the same manner as in Example 1, except that the amount of phthaloyl dichloride used was 2.1 tnt.

In addition, the titanium content in the solid catalyst component at this time is 562
He was in charge of weight. During the polymerization, an experiment was conducted in the same manner as in Example 1. The results obtained are shown in Table 1.

The yield (Φ) of the fully crystalline polymer is expressed by the following formula.

(D) = X10 0? %) Furthermore, the amount of residual chlorine in the generated M@rod body is meat

[Brief explanation of the drawing]

The figures are schematic diagrams to aid in understanding the invention.

Claims (1)

[Claims] 1) (I) After pulverizing the substance (a) obtained by reacting metal magnesium powder with at least twice the mole of alkyl monohalide in the presence of iodine and tetraalkoxytitanium (b). , tetraalkoxytitanium (b) to the obtained product at 70°C or higher in the presence of an aliphatic hydrocarbon (c),
Aliphatic alcohol (d) and phthalic acid dichloride (e
) are sequentially added and treated, and titanium tetrachloride (f) is added to the obtained product and further treated to obtain a solid catalyst component; (II) General formula SiR_m(OR')_4_-_m (In the formula, R is an alkyl group, a cycloalkyl group, a vinyl group, or an aryl group, and R' is an alkyl group. When R is an alkyl group, the alkyl group may be the same as R'. m is 0≦m<4.) A catalyst for polymerizing olefins, comprising a silicon compound represented by (III) an organoaluminum compound.