JPH0277406A - Catalyst for olefin polymerization - Google Patents

Abstract

PURPOSE:To provide the title catalyst capable of giving highly stereo-regular polymers having ordered shape, comprising a specific solid component containing Mg, Ti, alkyl monohalide, phthalic acid derivative and aliphatic alcohol, etc., Si compound and organoaluminum compound. CONSTITUTION:The objective polymerization catalyst comprising (A) a solid catalyst component, (B) a Si component of the formula (R is alkyl, vinyl or aryl; R' is alkyl; 0<=m<4), and (C) an organoaluminum compound. The component A can be prepared by the following processes: a mixture comprising (1) a substrate formed by reaction, in the presence of iodine, between metallic Mg powder and two or more molar times of an alkyl monohalide and (2) a phthalic diester is ground, and the resulting product is incorporated, in the presence of an aliphatic hydrocarbon, at >=70 deg.C, with a tetraalkoxytitanium, aliphatic alcohol and phthalic dichloride successively in this order to make respective treatments, and the resultant product is then incorporated with titanium tetrachloride to make a treatment.

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 (Natsu), a particular silicon compound (II), and an organoaluminium compound (2), as will be detailed later. It is.

[Prior art and its problems] Recently, instead of the well-known titanium trichloride catalyst component as a solid catalyst component in catalysts for polymerizing olefins such as globylene, a new type of catalyst component has been developed in which titanium, which is an active component, is chlorinated. Many compounds in which magnesium is supported together with an adult donor have been developed and proposed.

Among these, the earliest developed one was one in which a complex of an organic monocarbo/acid ester and titanium tetrachloride was co-pulverized with magnesium chloride as an electron donor. There is a co-milled product of organic monocarbo/acid ester and magnesium chloride treated with titanium tetrachloride.

However, when these are used in combination with organoaluminum compounds to industrially carry out the polymerization of olefins, especially the stereoregular polymerization of propylene, 1-butene, etc.5, when carrying out the polymerization reaction, organic monomers are used as electron donors. It is essential to use a carboxylic acid ester, and in this case, it is necessary to use an extremely large amount of an organic monocarboxylic acid ester, which poses the problem of imparting a characteristic ester odor to the resulting polymer. did.

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. 54-9459a 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 during the production of catalyst a# as well as during the polymerization. There is. Generally, the amount of organic carboxylic acid ester contained in the catalyst is reduced to such an extent that the odor problem of the produced polymer can be ignored by 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 liquid or gaseous monomers, almost all of it is Currently, it is contained in the produced polymer, and therefore, it can be said that the problem of raw M and the odor of the 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 insufficient for practical use in terms of performance and sustainability of activity. The reality is that it cannot be called a reality.

[Means to solve problems]

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

That is, Kinoe EJA provides a catalyst for polymerizing olefins, which is characterized by comprising a solid catalyst component (b) below, a silicon compound (M) below, and an organoaluminium compound (Qll) below.

(b) After pulverizing the substance (a) and phthalic acid diester (b)) obtained by reacting metallic magnesium powder with twice the mole or more of an alkyl monohalide in the presence of iodine, the resulting product is In the presence of aliphatic hydrocarbon (c), tetraalkoxytitanium (d), aliphatic alcohol (e) and phthalic acid dichloride (f) are sequentially added and treated at 70°C or higher, and the resulting product is Solid catalyst component obtained by adding titanium tetrachloride @ and further processing; (II) General 2 BARIn<OH2)4-m C
In the formula, Rri alkyl group, cycloalkyl group, vinyl group (9) is an aryl group, and R' is an alkyl group. R
When is an alkyl group, it may be the same as its alkyl base line R'. The present invention provides a catalyst for polymerizing olefins consisting of a silicon compound and an organoaluminum compound represented by -, where m is 06m (4).

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

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

In order to obtain the substance (hereinafter simply referred to as the substance (a)) obtained by reacting the metal magnesium powder and the alkyl monohalide in the presence of iodine in (a), commercially available metal magnesium powder and the alkyl monohalide are used. The alkyl monohalide is reacted in the absence of an organic solvent and in the presence of iodine. At this time, it is necessary to use 2 or more moles of the alkyl monohalide per 1 mole of the metal magnesium powder. In addition, 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. . This reaction is a Grignard type reaction.
When the spectrum is measured, absorption of alkyl groups can be seen.

The alkyl monohalides used in the production of the above (+L) substance are preferably chlorides of aliphatic hydrocarbons that are liquid at room temperature, such as n-propyl chloride, inglovir chloride, and n-butyl chloride. Examples include chloride, inbutyl chloride, pentyl chloride, pentychloride and octyl chloride.

Examples of the phthalic acid diesters (b) (hereinafter simply referred to as substance (b)) include dimethyl phthalate, diethyl phthalate, diisopropyl phthalate, diethyl phthalate, dibutyl phthalate, diynebutyl phthalate, cyamyl phthalate, diynamyl phthalate, and ethylbutyl hepthalate. , ethyl imbutyl 7 tallate, ethyl butyl 7 tallate, and the like.

The above (b) substance is CLO17 for (a) substance 1r.
The above is preferably used in a ratio of CLO1 to α2@t.

The aliphatic hydrocarbon (c) (hereinafter simply referred to as (f) substance) and the aliphatic alcohol (θ) (hereinafter simply referred to as (e) substance) are both liquid at -50°C to 50°C. There are 6 things.

((f) A preferable series of substances has 5 to 12 carbon atoms.
Aliphatic hydrocarbons such as bebutane, hexane, hepta/
, octane, nona/, decane, dodeca/, and isomers thereof, and a preferred series of (e) substances include aliphatic alcohols having 2 to 10 carbon atoms, such as ethanol, gropanol, butanol, be/tanol. , hexanol, octatool and their isomers.

Tetraalkoxytitanium of (d) above (hereinafter simply (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 type or two or more types of tetraalkoxytitanium can be used. (d) Substance usage t is typically in the range [11 to 10 fO in total for (a) Substance 12.

The phthalic acid dichloride (f) is used in a ratio of α05 to substance 11 (a), preferably α1 to α5t.

The titanium tetrachloride [Co., Ltd.] used in the present invention is (&
) It is used at a ratio of 1f or more, preferably ri5F or more, to 1f of the substance.

The contact temperature at this time is usually #'i, not less than a°C and not more than 150°C. The contact time is at least 10 minutes, preferably at least 30 minutes.

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

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 (b) in the present invention is preferably carried out in the absence of oxygen, moisture, and the like.

The solid catalyst component (I) prepared as above is combined with the silicon compound (■) and the organoaluminum compound (side) to constitute the catalyst for polymerizing olefins according to the present invention. Examples of the silicon compound of (II) include alkoxysilane, phenylalkoxysilane, alkylalkoxysilane, cycloalkylalkoxysilane, cycloalkylalkoxysilane, and specifically tetramethoxysilane,
Tetraethoxysilane/, phenyltrimethoxysilane,
Phenyl Torie) -? Disilane, phenyltripropoxysilane, phenyltriingloboxysila/, diphenyldimethoxysilane, diphenyljethoxysilane,
Examples include ethyltriethoxysilane, ethyltriethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, ethyltriisogropoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, divinyljethoxysilane, and divinyldimethoxysilane. can.

Examples of the organoaluminum compound in (2) above include trialkyl, aluminum, dialkyl aluminum halide, alkyl aluminum sinolide, alkyl aluminum sinolide, and mixtures thereof. Among them, trialkyl aluminum is preferable. Furthermore, triethylaluminum and triimbutylaluminum are particularly preferred.

The organoaluminum compound (b10) contains 1 to 1,000 titanium per atom in the solid catalyst component,
The silicon compound is used in a molar ratio of 1 or less to the organoaluminum compound, preferably in the range of rj:α005 to to.

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. The polymerization temperature is 20
The temperature is 0°C or lower, preferably 100°C or lower, and the polymerization pressure is 1
00 to 9/ffi”・q or less preferably 50 yu/sub 2・
G or less.

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

[Action and effect of 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. 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 adhesion to the resulting silica.

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 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 allow hydrogen to coexist during the rt oxidation process from the viewpoint of controlling the M process. Catalysts using acid esters have the disadvantage that their activity and stereoregularity are significantly reduced in the presence of hydrogen. 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 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 undesirable fine powder polymers during the manufacturing process of VORIOLEFY/, making it suitable for gas phase polymerization, which has been attracting attention recently, and has excellent 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.

[Implementation row]

The present invention will be explained in more detail below by way of examples.

Example 1 (Preparation of b1 (+L) substance) Using a round-bottomed flask with a capacity of 100 ml and equipped with a stirrer, after sufficiently replacing the flask with nitrogen gas, metallic magnesium powder 302, iodine 1.0?, and n- 1.21 f of butyl chloride was charged, and the reaction was carried out for 5 hours at the boiling point of n-butyl chloride.After the reaction was completed, the supernatant liquid was removed, and the product was washed three times with 500mcDn-butyl chloride, and then dried under reduced pressure. A powdery substance was obtained.

(2) Preparation of solid catalyst component The powdery substance obtained in (b) above 30? and n-butyl 7-talate 1.5- in a nitrogen gas atmosphere, 25wIφ
A stainless steel pole was placed in a vibrating mill pot with a volume of ztot filled with % of the total volume, and the vibration frequency was 1430 v, p, m.
, with a shaking width of 5-5 for 17 hours.

In a 500-capacity round bottom flask equipped with a stirrer, 10f, n-deca/70-
Then, the temperature was raised to 80℃, and 12-
was charged, the temperature was raised to 125°C, and treatment was carried out for 1 hour while stirring. This was then added with n-hebutane 25-,! :2-
7.1m of hexyl alcohol! 'ii The combined solution was added dropwise over a period of 30 minutes and reacted for 1 hour while maintaining the temperature at 125°C.

Thereafter, it was cooled to 80°C, and a mixed solution of 25@t of n-heptane and 1.7 wLt of phthaloyl dichloride was added at 30°C.
It was added dropwise over a period of 1 minute, and the temperature was raised to 90°C and treated for 1 hour. The obtained A7 product was washed 5 times with 200 d of hebutane, then TiO4,75- was added and the product was incubated at 115°C for 3
Allowed time to react. After the reaction was completed, 200 m of hebutane was added for 10
A solid catalyst component was obtained by washing twice.

At this time, when the content of the solid catalyst component was measured, it was found to be 488% by weight.

(3) Polymerization content of propylene A Hzot autoclave equipped with a stirring device was used, and after the autoclave was completely replaced with nitrogen gas, 200 q of triethylaluminum, 45 q of diphenyldimethoxysilane, and the solid catalyst component away were charged. Thereafter, hydrogen gas tatzied propylene taZ was charged, and a polymerization reaction was carried out at 70° C. for 1 hour. After the completion of the coalescence reaction, the produced polymer was dried under reduced pressure at aO℃, and the amount of the obtained product was expressed as (A
). Further, this product is extracted with boiling n-hegetane for 6 hours to obtain a compound insoluble in n-hegetane, and the amount of this product is designated as ω].

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

The yield Φ of the dead gold crystalline polymer is expressed by the following formula.

Furthermore, the amount of residual chlorine in the produced polymer is represented by @), and the M process of the produced polymer is represented by (F), and the obtained results are shown in Table 1.

Experimental Row 2 An experiment was conducted in the same manner as in Example 1 except that the deposit time was 60 minutes. The results obtained are shown in Table 1.

Example 5 An experiment was carried out in the same manner as in Example 1 except that the same amount of dibutyl phthalate was used instead of dibutyl phthalate.

In addition, the titanium content in the solid catalyst component at this time was &97
I got killed by the weight clerk.

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

The results obtained are shown in table 1 for 1 prefecture.

1st ceremony

[Brief explanation of the drawing]

The m1 diagram is a schematic drawing to help solve the problem of the present invention.

Claims (1)

[Claims] 1) (I) After pulverizing the substance (a) and phthalic acid diester (b) obtained by reacting metallic magnesium powder with twice or more moles of alkyl monohalide in the presence of iodine. , Tetraalkoxytitanium (d), aliphatic alcohol (e) and phthalic acid dichloride (f) are sequentially added to the obtained product in the presence of an aliphatic hydrocarbon (c) at 70°C or higher for treatment, respectively. , a solid catalyst component obtained by adding titanium tetrachloride (g) to the obtained product and further processing; (II) General formula SiR_m(OR')_4_-_m (wherein R is an alkyl group, cyclo R' is an alkyl 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. ) and (III) an organoaluminum compound.