JPS6341510A - Catalyst for polymerizing olefins - Google Patents

Abstract

PURPOSE:To obtain the titled novel catalyst having extremely high activity and small reduction in activity, providing a highly stereoregular polymer having an extremely small amount of catalytic residue and residual chlorine, consisting of a specific solid catalytic component, a specific piperidine derivative and an organoaluminum compound. CONSTITUTION:First, (A) a substance obtained by reacting metallic Mg powder with >=2mol alkyl monohalide (preferably octyl chloride, etc.) in the presence of a dialkoxy magnesium and (B) a phthalic acid diester and (C) TiCl4 are ground together and the reaction product is brought into contact with the compo nent C to give a solid catalytic component. Then the solid catalytic component is combined with a disubstituted or tetrasubstituted piperidine derivative (prefer ably 2,2,6,6-tetramethylpiperidine) shown by the formula (R<1>-R<4> are H, replace able alkyl with the proviso that at least one of R<1> and R<2> or at least one of R<3> and R<4> is alkyl) and an organoaluminum compound (preferably triethylaluminum, etc.), to give the aimed catalyst.

Description

[Detailed description of the invention] [Industrial application field] The present invention is applied to the polymerization of olefins.

The present invention relates to a high-performance catalyst that acts with high activity and can produce stereoregular polymers in high yield. More specifically, the present invention provides a material obtained by co-pulverizing a material obtained by reacting a metallic magnesium powder and an alkyl monologinide in the presence of dialkoxymagnesium, and a diester of phthalic acid and T i Ot4. The product that is
The present invention further relates to a catalyst for polymerizing olefins comprising a solid catalyst component obtained by contacting with T i Ot4, a di- or tetrasubstituted piperidine derivative, and an organoaluminum compound.

[Prior art]

Recently, instead of the conventionally well-known titanium trichloride catalyst component as a catalyst for the polymerization of olefins such as propylene, many new types of catalysts have been developed in which the active component titanium is supported on magnesium chloride together with an electron donor. 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 magnesium chloride, or a complex of an organic monocarboxylic acid ester as an electron donor and titanium tetrachloride, or There is a co-milled product of acid nysterte with magnesium chloride treated with titanium tetrachloride.

However, since these are used on an industrial scale, K cannot be said to have satisfactory properties, and there are methods to improve various properties, such as those using jetoxymagnesium instead of magnesium chloride, and special K as an electron donor. Various methods have been proposed in which compounds are used, or methods of combining the 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,
Organoaluminum compound.

A method for polymerizing olefins using a combination of an organic carboxylic acid ester and a compound having an M-0-R group has been disclosed. A method is disclosed in which a catalyst component is prepared by combining esters, active magnesium chloride, and a titanium compound, and propylene is further polymerized using a compound having a 51-0 bond or an Eli-N bond and an organoaluminum compound. ing.

[Problems to be Solved by the Invention] In the prior art, chlorine contained in magnesium chloride, which is the main carrier material, and titanium halide) and chlorine contained in titanium halides). However, since magnesium chloride has the disadvantage of having an adverse effect, countermeasures have been taken to counter this, such as requiring high activity to the extent that the effect of chlorine can be virtually ignored, or reducing the concentration of magnesium chloride itself. ing.

In addition, when carrying out industrial polymerization of olefins, especially stereoregular polymerization of propylene, 1-butene, etc., using the catalyst component having magnesium chloride as a carrier in combination with an organoaluminum compound, when carrying out a single polymerization reaction, It is essential to use an organic monocarboxylic 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 as magnesium chloride carriers, although the activity is high at the initial stage of polymerization, deactivation over time causes problems in process operation, and block copolymerization For longer polymerization times, it was virtually impossible to use it.

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 during catalyst preparation and during polymerization. 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 in one 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 the Currently, 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 it is extremely difficult.

The present inventors conducted extensive research in order to solve the various problems in the prior art, and succeeded in providing a novel catalyst for polymerizing olefins.

[Disclosure of the invention]

The present invention comprises (A) (a) a substance obtained by reacting a metal magnesium powder and an alkyl monohalide in an amount of twice the mole or more in the presence of dialkoxymagnesium; (b) a diester of phthalic acid and U ( c) Solid catalyst component obtained by further contacting the product obtained by co-pulverizing Tiet4' with TiOt4: 03) General formula (wherein R1, R11, R3, R4 are hydrogen or substituted an alkyl group which may have a group, at least one of R1 and R2 is an alkyl group, and R3
At least one of and R4 is an alkyl group. The present invention provides a catalyst for polymerizing olefins, which is characterized by comprising a di- or tetrasubstituted piperidine derivative represented by (C) and an organoaluminum compound (C).

In order to obtain the substance obtained by reacting the metal magnesium powder and the alkyl monohalide in the above (1) in the present invention in the presence of dialkoxymagnesium (hereinafter simply referred to as substance (a)), commercially available metal magnesium powder and an alkyl monohalide in the presence of dialkoxymagnesium. At this time, it is necessary to use 2 mol or more of the alkyl monohalide per 1 mol of metal magnesium powder, and dialkoxymagnesium It is necessary to use α1 to α21 per ton of magnesium powder. Further, 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, and when the R spectrum of the substance (a) obtained in the first reaction is measured, absorption of alkyl groups is observed.

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

The dialkoxymagnesium used in the production of the substance (a) is preferably one having an alkyl group having 1 to 5 carbon atoms, such as jetoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, and the like.

In the present invention, the diesters of phthalic acid (b) include dimethyl phthalate, diethyl phthalate, diisopropyl phthalate, dipropyl phthalate, dibutyl hepthalate, diisobutyl phthalate, cyamyl phthalate, diisoamyl phthalate, ethyl butyl phthalate, ethyl isobutyl phthalate, and Examples include ethylpropyl phthalate.

In the present invention, the piperidine derivatives (g) above are preferably di- or tetrasubstituted derivatives, and specifically, the general formula (wherein R1, R2, R3, and R4 are hydrogen or have a substituent) an alkyl group which may be

At least one of R1 and R2 is the alkyl group, and at least one of R3 and R4 is the alkyl group.

). More specific examples include 2.6-diitupropylpiperidine, 2.6-sibutylpiperidine, 2.2. & 6-titramethylbiveridine 4 2,2. /), 6-titraethylbiveridine.

Among them, 2.2.6.6-
Citramethylbiperidine is preferred.

Examples of the organoaluminum compound (C) in the present invention include trialkylaluminum, dialkylaluminum halide, alkylaluminum civalide, and mixtures thereof. Among them, trialkylaluminum is preferred, and triethylaluminum is more preferred. and triisobutylaluminum are particularly preferred.

When obtaining the solid catalyst component (A) in the present invention, the proportion of each raw material constituting the solid catalyst component is arbitrary as long as it does not adversely affect the performance of the solid catalyst component to be produced. Usually, but not limited to (a
) Substance 1PK, the above (b) diester of phthalic acid (hereinafter simply referred to as (b) substance) is Q, 01
~1f, and the above T i C1, is (a)
When co-pulverizing the substance and (b) substance, Q
, 01 to 1f, and in the case of contact with the product obtained by the co-pulverization, it is in the range of 0.1f or more, preferably 19 or more.

(a) substance, (b) substance and (c) Ttcz,
The co-grinding is usually carried out for 10 minutes or more, preferably 30 minutes or more.

Contact between the composition obtained by the co-pulverization and TlC1° is preferably carried out at a boiling point temperature range of -10°C to 'r1c4 for 10 minutes to 100 hours.

The composition obtained after contacting as described above is further added with T5.
Cts can be contacted. Moreover, the obtained composition can also be washed using an organic solvent such as n-hebutane. All of these are included in one embodiment of the implementation of the present invention.

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

The solid catalyst component (A) prepared as described above is combined with the piperidine derivative (B) and the organoaluminum compound (C) to constitute the catalyst for polymerizing olefins according to the present invention. .

The organoaluminum compound (0) is used in an amount of 1 to 1,000 mol per titanium in the solid catalyst component, and the piperidine derivative has a molar ratio of 1 or less, preferably [1,005 to 1.0] to the organoaluminum compound. Used within the range of

The polymerization reaction using the polymerization catalyst of the present invention can be carried out in the presence or absence of an organic solvent, and the olefin monomer used can be used in either gas or liquid state. Can be done. The polymerization temperature is 2
The temperature is 00° C. or lower, preferably 100° C. or lower, and the polymerization pressure is 1001° C. or lower, preferably 50 kg/F2.G or lower.

When olefins are polymerized using the olefins that are homopolymerized or copolymerized using the catalyst for olefins polymerization according to the present invention, the olefins exhibit a higher activity than previously expected. Catalyst residues present in polymer 11
Furthermore, 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.

Furthermore, according to the present invention, by not adding an organic carboxylic acid ester during polymerization, the major problem of ester odor attached to the resulting polymer can be solved.

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 significantly as the polymerization progressed, but the catalyst according to the present invention The decrease in activity over time is extremely small compared to conventionally known catalysts, making it useful for longer polymerization times such as copolymerization, and when using higher polymerization pressures. Since the increase in activity is large, 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 high degree of stereoregularity can be obtained.

Additionally, in the industrial production of olefin polymers, it is common to allow hydrogen to coexist during polymerization from the viewpoint of M process control, but conventional magnesium chloride is used as a carrier.

Catalysts using organic carboxylic acid esters have the disadvantage that their activity and stereoregularity are 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 M of the produced polymer is
Activity and stereoregularity are not reduced even when I is very high. Such effects are strongly recognized by those skilled in the art.
It was something that was 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., and the catalyst according to the present invention also has this problem. , has extremely excellent properties]7.

[Examples, Comparative Examples] The present invention will be explained in more detail below using Examples and Comparative Examples.

Example 1 (1) (a) Preparation of substances Using a round bottom flask equipped with a stirrer, the flask was sufficiently purged with nitrogen gas.

Metallic magnesium powder 30y, diet magnesium l,,0? and 1.21 k of n-butyl chloride were charged, and the mixture was reacted under reflux for 5 hours.

After the reaction was completed, the supernatant liquid was completely removed and the product was heated to 500 d of n-
After washing with butyl chloride three times, the product was dried under reduced pressure to obtain powdered substance (a).

(2) Preparation of solid catalyst component 20 parts of the powdered material obtained in the above (]), dibutyl phthalate 7.0- and Ti0 6.4.0- were mixed in a 25 φ stainless steel ball under a nitrogen gas atmosphere. The mixture was placed in a vibrating mill pot with a capacity of 1.0 t filled with the entire volume, and co-pulverized for 17 hours at a vibration frequency of 1430 V-p, m and an amplitude of 3.5 μm.

Using a 500-capacity round bottom flask equipped with a stirrer,
After sufficient substitution with nitrogen gas, take the solid composition 51 obtained by the co-pulverization treatment, and add Tl to it.
Add C14200m/.

The temperature was raised to 120°C and the mixture was reacted for 2 hours. Remove the supernatant from reaction path 1 and remove the product (new KTi, C1a200
d was added and the reaction was continued at 120°C for 2 hours.

After the reaction was completed, the reaction mixture was cooled to 40° C. and washed with 200 d of product ♀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 2.76%.

(3) Polymerization internal volume2. Using an O4 autoclave with a stirrer, the autoclave was completely replaced with nitrogen gas, and after fc, triethylaluminum 193% to 2.2.6.6-titramethylbiveridine 24jv and pre-H (solid catalyst component 50 After that, 1.1 liters of hydrogen gas and 1.4 tons of liquefied propylene were charged, and a polymerization reaction was carried out at 70°C for 1 hour. After the polymerization reaction was completed, the produced polymer was dried under reduced pressure at 80°C. The resulting product is expressed as il: Th (A). The crushed product is extracted with boiling n-heptane for 6 hours to obtain the entire polymer that is insoluble in n-heptane, and the m of this product is (B). shall be.

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

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

Furthermore, the residual chlorine content in the produced polymer was expressed as the amount of residual chlorine (@), the M'e (F), and the electrical ratio M'k (G) of the produced polymer, 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 The following procedures were carried out except that the polymerization reaction was carried out in the following manner [+i 1
An experiment was conducted in the same manner.

Into an autoclave with an internal volume of 2.0 t and equipped with a stirrer, which was completely purged with nitrogen gas, 700 - of n-hebutane was charged,
Triethyl aluminum 30 while maintaining nitrogen gas atmosphere
1~. 2.2.46-Tetramethylpiperidine 37MI
y, then solid catalyst component i1 prepared by the method of Example 1
0. Dq was charged. After that, charge hydrogen gas j50-7
0℃KJ [and while introducing propylene gas, to 6/,
?・The polymerization reaction was carried out for 1 hour while maintaining the pressure of G.

After the polymerization reaction is completed, the obtained solid polymer is stored at 80°C.
and dried under reduced pressure.

On the other hand, the amount of the polymer dissolved in the polymerization solvent after condensing the P solution is defined as (), and the solid polymer is defined as i'k (I).

Further, the obtained solid polymer was extracted with boiling n-hebutane for 6 hours to obtain a polymer insoluble in n-hebutane. !
Let r be (J).

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

Further, the yield (L) of the crystalline polymer is expressed by the following formula, and the yield (M) of the total crystalline polymer '! r is determined by the following formula.

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

Example 4 An experiment was conducted in the same manner as in Example 3, except that the polymerization time was 2 hours. The results obtained are shown in Table 2.

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 2.7
1 was in charge of weight.

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

The results obtained are shown in Table 1.

Example 6 The solid catalyst component was prepared in the same manner as in (2) of Example 1, except that the reaction (twice) after adding TiCt, 20 [1-, was carried out at 130 ° C. Ta.

In addition, the titanium content in the solid catalyst component at this time was 2.5
1 was in charge of weight. During polymerization, an experiment was conducted in the same manner as in Example 1.

The results obtained are shown in Table 1.

Table 1 Table 2 For comparison, cases based on the prior art are listed below as Comparative Examples 1 and 2.

Comparative Example 1 Commercially available MgCJ420 f/, dibutyl phthalate SO
- is crushed under the same conditions as in Example 1. Thereafter, the pulverized composition 52 was charged into a glass container having an internal volume of 500 mm under a nitrogen gas atmosphere, and TiCt was obtained.

20 rows were added and the entire reaction was carried out with stirring at 120°C for 2 hours. After the reaction was completed, the supernatant was removed and a new TiC4200-
was added and reacted at 120°C for 2 hours.

After the reaction was completed, it was cooled to 40°C and added with 200 barrels of n-hebutane.
It was washed 0 times to obtain a solid catalyst component.

At this time, the titanium content in the solid catalyst component was measured and found to be 1.64% by weight.

An experiment was carried out in the same manner as in Example 1 except that &OIng of the above solid catalyst component was used during the polymerization. The results obtained are shown in Table 3.

Comparative Example 2 An experiment was conducted in the same manner as Comparative Example 1 except that the polymerization time was 30 minutes. The results obtained are shown in Table 3.

Table 3

[Brief explanation of the drawing]

FIG. 1 is a schematic drawing to aid in understanding the present invention.

Claims (1)

[Claims] (1) (A) (a) Substance obtained by reacting metallic magnesium powder with twice or more moles of alkyl monohalide in the presence of dialkoxymagnesium, (b) Diester of phthalic acid, and (c)
The product obtained by co-pulverizing TiCl_4 is further
Solid catalyst component obtained by contacting with iCl_4; (B) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R^1, R^2, R^3, R^4 are hydrogen or It is an alkyl group that may have a substituent, and at least one of R^1 and R^2 is an alkyl group, and at least one of R^3 and R^4 is an alkyl group.) A catalyst for polymerizing olefins, comprising a di- or tetra-substituted piverdine derivative represented by the following formula and (C) an organoaluminum compound.