JPS63210103A - Solid catalyst component for polymerizing olefins - Google Patents

Abstract

PURPOSE:To provide the title catalyst component which can produce a stereoregular polymer in a high yield, by contacting a liquid aromatic hydrocarbon in which diethoxymagnesium is suspended with TiCl4 in the presence of an aromatic dicarboxylic acid diester and CaO. CONSTITUTION:Diethoxymagnesium (A) and CaO (B) in an amount of 0.5-1.5pts. wt. ratio to component (A) are ground together, and the resulting composition is contacted with an aromatic hydrocarbon (D) (e.g., toluene) which is liquid at ordinary temperatures, and TiCl4 (E) in an amount of 1g or more for 1g of component (A) in the presence of a diester of an aromatic dicarboxylic acid (e.g., dimethyl terephthalate) in an amount of 0.05-10mol. for 1g of component (A) plus component (B) at 0-136 deg.C for 5min-100hr, and then contacted with component (E) in an amount of 1g or more for 1g of component (A) to produce a solid catalyst component for polymerizing olefins.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a solid catalyst component for the polymerization of olefins.

More specifically, the present invention acts with high activity in the polymerization of olefins.

Moreover, it provides a solid catalyst component for a catalyst that can obtain a stereoregular polymer in an extremely high yield, and in particular, it provides a catalyst for polymerizing olefins that has an amazingly high polymerization activity per T1 in the catalyst component. Related to solid catalyst components.

[Conventional technology and its problems]

Conventional catalysts for polymerizing olefins with high activity content include:
A combination of a solid titanium halide and an organoaluminum compound as a catalyst component is well known and widely used.
However, the catalyst component and the yield of polymer per titanium in the catalyst component are low, and so far, efforts have been made to increase them.
Many studies have been conducted. In particular, if the yield of polymer per titanium is low, the titanium component remaining in the polymer will have a strong corrosive effect that will not only lead to total wear and tear of the polymerization equipment and various equipment used in the post-treatment process, but also damage to the produced polymer itself. It is well known that it causes various adverse effects such as deterioration and yellowing, and a solution to this problem has been strongly desired in the industry. Is the titanium content in the catalyst component a means of achieving this? To reduce or
Research has been carried out to solve this problem by increasing the yield of polymer per catalyst component, but none of these methods have yielded satisfactory results. Demineralization process? It was often necessary. Since this deashing process uses a large amount of alcohol or chelating agent, recovery equipment or regeneration equipment is indispensable, and there are many accompanying problems in terms of resources, energy, etc., and it cannot be operated on an industrial scale. This was considered an important issue in the case.

In addition, various attempts have been made to solve the above problems, but in general, if the titanium content in the catalyst component is kept low, the yield of polymer per catalyst component decreases, and the yield of polymer per catalyst component decreases. Attempting to increase the titanium content in the catalyst component increases, and the yield of polymer per titanium therefore decreases.

For example, in Japanese Patent Publication No. 56-52041, Teha, magnesium halide and periodic table 11■,
Attempts have been made to reduce the titanium content in the catalyst component and increase the activity per titanium by contacting anhydrous compounds of the above group, but as a result, the polymerization activity per catalyst component is extremely low. The polymerization activity is also not sufficient. In addition, the applicant has previously proposed a patent application filed in 1986-
No. 000045, a dialkoxymagnesium, such as jetoxymagnesium, is suspended in an aromatic hydrocarbon and then contacted with a titanium halide, and the resulting product is further contacted with a titanium halide, At some point in this process, they succeeded in dramatically increasing the polymerization activity per catalyst component by contacting the aromatic dicarboxylic acid with a diester, but due to the high titanium content in the catalyst component, The polymerization activity does not show a fully satisfactory value.

The high content of titanium in the catalyst component here means that the amount of organoaluminum compound used during polymerization is
/T1 molar ratio, a substantially large amount of organoaluminum compound is used, and even if the catalytic activity shows a somewhat high value, the catalyst is Will it lead to an increase in the basic unit of production? It means.

[Purpose of the invention]

The present invention suppresses the titanium content in the catalyst component to solve the problems in the prior art.

Moreover, it is an object of the present invention to provide a solid catalyst component of a catalyst for offfin polymerization that can increase the yield of polymer per catalyst component and, as a result, dramatically increase the polymerization activity per titanium.

[Disclosure of the invention]

According to the invention, the product obtained by suspending jetoxymagnesium (a) in an aromatic hydrocarbon which is liquid at room temperature) and subsequently contacting it with titanium tetrachloride (c) is added to a)? At this time, the aromatic dicarboxylic acid diester (d) and calcium oxide (e) are made to coexist in any of the steps of the suspension and/or contact, and the calcium oxide (e) is made to coexist with jetoxymagnesium. (,) in weight ratio (L5~
A solid catalyst component for polymerizing olefins obtained by using the catalyst at a ratio of t5 is provided.

The present invention will be explained in detail below.

The dialkoxymagnesium of (a) (hereinafter simply referred to as (a)
) Substances) include jetoxymagnesium, dibutoxymagnesium, diphenoxymagnesium, dipropoxymagnesium, di-5ea-butoxymagnesium, di-butoxymagnesium and diisopropoxymagnesium, among which jetoxymagnesium and dipropoxymagnesium is preferred.

Aromatic hydrocarbons (hereinafter simply referred to as ()) that are liquid at room temperature (b) above
Examples of the substance b) include benzene, toluene, xylene%1.2-dichloroethane, orthodichlorobenzene, and the like. Among these, toluene is a preferred substance.

The diester of aromatic dicarboxylic acid (hereinafter simply referred to as (d) substance) is preferably a diester of phthalic acid or thenphthalic acid, such as dimethyl phthalate, dimethyl terephthalate, diethyl phthalate, diethyl terephthalate, dipropyl phthalate, dimethyl phthalate, etc. Propyl terephthalate, dibutyl phthalate, dibutyl tenphthalate)% Diisobutyl phthalate, cyamyl phthalate, diynamyl phthalate, ethyl butyl phthalate, ethyl isobutyl phthalate, and ethyl butyl phthalate Each raw material when preparing the solid catalyst component storage according to the present invention The ratio of the substances to be used is that the calcium oxide (hereinafter simply referred to as (θ) substance) in (e) is used at a weight ratio of (15 to t5) to the substance (a).For each other substance, Although not specified as long as it does not adversely affect the performance of the solid catalyst component obtained, 1 usually the above (C) titanium tetrachloride C (hereinafter simply referred to as (c) substance) with (a) substance or ( During the initial contact between the a) substance and the (6) substance, the range is 12 or more, preferably 2F or more, relative to 1 fVC of the (a) substance. (b) The substance is
It is arbitrary as long as it can form a suspension with the substance (a) or a suspension between the substance (a) and the substance (θ). Also,(
d) The substance is 105 to 10 mmO4%, preferably α2 mmot to 5 per 1 ton of the (a) substance and (8) substance.
mmot ◎(c) The amount to be used for re-contacting the substance is the same as for the first contact, (a) 1f of the substance
1f or more, preferably 22 or more.

Although the order and method of contacting each substance to obtain a solid catalyst component are not specified, preferred embodiments will be described below. In a first preferred embodiment, after co-pulverizing the (a) substance and (e) substance with a Kurura vibration mill or the like, the resulting composition is (a)
Examples include a method of contacting the substance (b) and the substance (c) in the presence of the substance, and then contacting the substance anew with the substance (c). In a second preferred embodiment, (a) the substance and (e) the substance are suspended in the (b) substance, and then brought into contact with the (c) substance in the presence of the a) substance, and then freshly (
c) A method of contacting with a substance is mentioned.

The temperature of contact between (a) substance, (b) substance and (c) substance is usually in the temperature range of Ω°C to 136°C, and the contact time is 5 minutes to 100 hours, preferably 5 minutes to 10 hours. It is a range of time. After that contact, the product (
b) Repeated washing with substances and other organic solvents is possible. The subsequent contact treatment with the substance (c) is carried out under the same conditions as the first contact treatment. The above substance (b) may be used alone or in combination with other organic solvents. After completing these treatments, the product is
If necessary, it is possible to wash with an organic solvent such as n-hebutane.

The solid catalyst component prepared as described above is combined with an organoaluminum compound and used as a catalyst for polymerizing olefins. It is also a preferred embodiment to use an electron-donating compound such as an organosilicon compound during polymerization.

The polymerization reaction can be carried out in the presence or absence of an organic solvent. The olefin monomer used can be used in either gas or liquid state. The polymerization temperature is 200C or less, preferably 100C or less, and the polymerization pressure is 100Y7cm".G or less, preferably 50YU/G or less.
The fall is 3.G or less.

Olefins to be homopolymerized or copolymerized using the solid catalyst component according to the present invention include ethylene, propylene,
Examples include 1-butene.

〔Effect of the invention〕

When polymerizing olefins using the catalyst of the olefin solid catalyst component according to the present invention, the amount of polymer per solid catalyst component is The yield (polymerization activity per catalyst component) is extremely high, and the residual titanium content in the produced polymer is completely negligible, so there is almost no need for a deashing process, and there are almost no problems such as deterioration or yellowing of the produced polymer. Does not occur.

Also, At in organoaluminum compounds normally used in the polymerization of olefins.

In many cases, the T10 molar ratio, that is, the ht7'rx molar ratio in the solid catalyst component is set within a certain range, but in such cases, the solid catalyst component according to the present invention has an extremely low titanium content. Despite this, A4/T1
Since a very high yield of polymer per catalyst component can be obtained without changing the molar ratio, the amount of organoaluminum compound used can be reduced, leading to a reduction in cost when considered per total catalyst.

Furthermore, since the catalyst using the solid catalyst component according to the present invention contains a smaller amount of chlorine than conventionally known catalysts, the amount of residual chlorine in the produced polymer can be kept extremely low. This residual chlorine, like T1, is avoided by those skilled in the art because it has a strong corrosive effect, but the present invention can also solve this problem.

Furthermore, when olefins are polymerized using the catalyst of the solid catalyst component according to the present invention, the decrease in activity over the course of polymerization is extremely small, the yield of stereoregular polymer is high, and hydrogen The special effect of solving the problem of a decrease in the yield of active and stereoregular polymers in coexistence can also be obtained.

[Examples and comparative examples]

The present invention will be explained in more detail below with reference to Examples and Comparative Examples.

Example 1 1) Preparation of solid catalyst components Calcium oxide 309 and Jetoxymagnesium 4
511 (, fully purged with nitrogen gas, charged into a vibrating mill pot with a capacity of t2t filled with 25 φ stainless steel balls % of the total capacity, and heated at a vibration frequency of 1430 vpm and a shaking width of 55cm). The pulverization treatment was carried out at room temperature for an hour. In a 500-capacity round bottom flask, which was sufficiently purged with nitrogen gas and equipped with a stirrer, 9 tons of the composition obtained by the above pulverization treatment and 50 tons of toluene were placed, and the mixture was stirred. Mix and contact for 5 minutes. Then add Tiet, 50 d, and heat at 90°C.
The temperature was raised to 115°C, and n-dipyl phthalate L9f was added thereto, and the mixture was further heated to 115°C and reacted with stirring for 2 hours. The obtained solid product was separated by F, and freshly added 10% of toluene.
0- at 90°C, then Ti0t4
40- and toluene 6O- were added, and the mixture was reacted with stirring at 115° C. for 2 hours. After the reaction was completed, the reactor was cooled to 4°cj and washed repeatedly with n-hebutane. When chlorine was no longer detected in the washing waste liquid, the washing was completed and a solid catalyst component was obtained.

At this time, when the solid and liquid in the solid catalyst component were separated and elemental analysis of the solid content was performed, it was found that the weight of each component was 31% Teoa.
25,? , Mg11.9, Ol 5a6, TiLll.

2) Charge 700 d of n-heptane into an autoclave with a stirrer and an internal volume of ZOt that has been completely purged with polymerized nitrogen gas, and add 181 d of triethylaluminum while maintaining a nitrogen gas atmosphere.
! , phenyltriethoxysilane 38 and then the solid catalyst component was charged as titanium atoms [13q]. After that, 120 dl of hydrogen gas was charged, the temperature was raised to 70°C, and while propylene gas was introduced, 6 kli/a+" 6 G
The polymerization reaction was carried out for 2 hours while maintaining the pressure of .

After the polymerization reaction was completed, the obtained solid polymer tF was separated, heated to 80° C., and dried under reduced pressure. On the other hand, the amount of polymer dissolved in the polymerization solvent after condensing the filtrate is defined as It (A).

Let the amount of solid polymer be φ). Further, the obtained solid polymer was extracted with boiling n-heptane for 6 hours to obtain a polymer insoluble in n-heptane, and this amount was defined as t (c).

The polymerization activity per T1 in the solid catalyst component is expressed by the formula.

Further, the yield (total) of the crystalline polymer was expressed by a formula and determined from the total yield (IF) of the crystalline polymer. Moreover, the M process of the produced polymer is represented by (G). The results obtained are shown in Table 1.

Example 2 A solid catalyst component was prepared in the same manner as in Example IIIB column 1 except that the amount of n-diptylphthalate was 2.2f. In addition, when the solid and liquid in the solid catalyst component were completely separated and elemental analysis of the solid fraction was performed, it was found that the weight [1 and Oa
248. Mg 12.1, Ol 37.9, Ti
It was 1.18.

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

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 diphenyldimethoxysilane 59 wg f was used instead of phenyltriethoxysilane during polymerization. The results obtained are shown in Table 1.

Example 4 1) Preparation of solid catalyst component A reactor with a capacity of 500, sufficiently purged with nitrogen gas and equipped with a stirrer.
- Take calcium oxide Sat, jetoxymagnesium 4.5f and toluene 50- in a round bottom flask,
Leave in contact with stirring for 1 hour at 0°C. Then TiO450
al was added, the temperature was raised to 90°C, n-butyl phthalate t9F was added, the temperature was further raised to 115C, and the mixture was reacted with stirring for 2 hours. The obtained solid product was washed separately with F at 90°C using 100° of toluene, and further added with 10440° of T10440 and 60° of toluene.
The reaction was carried out at C for 2 hours with stirring. 40℃ after completion of reaction
cooled to
When chlorine was no longer detected in the washing waste liquid, the washing was completed and a solid catalyst component was obtained. At this time, the solid and liquid in the solid catalyst component were separated and elemental analysis of the solid fraction was performed, and the weight ratios of 0a2Fk, 2, Mg12. ．． 5
．． It was 0t31L2, 'l'ii, 07.

2) Polymerization For polymerization, an experiment was conducted in the same manner as in Example 1. The results obtained are shown in Table 1.

Comparative Example 1 When preparing the solid catalyst component, calcium oxide was not used, and jetoxymagnesium f9t and n-dibutyl phthalate were used at 2
, 5F was used, but the experiment was conducted in the same manner as in Example 4. At this time, when the solid and liquid in the solid catalyst component was separated and elemental analysis of the solid fraction was performed, the weights of each were 18 Mg, 62 Ot, and 512 T1, which was 9.

An experiment was carried out in the same manner as in Example 1, except that the solid catalyst components used in the polymerization were 0.5q as titanium atoms, 301q of ethylaluminum, and 64xg of phenyltriethoxysilane. The results obtained are shown in Table 1.

Comparative Example 2 1) Preparation of solid catalyst component Anhydrous Mg0J4 +i 5 ? , anhydrous Li0t40
f and Ti0t4! L 4 f was placed in a vibrating mill pot with a capacity of 1.0 t filled with 25-1 stainless steel balls in % of the total volume under a nitrogen atmosphere, and the vibration frequency was 1460.
Grinding was carried out for 16 hours at Vpm and shaking width of 55mm.

Capacity 50, fully purged with nitrogen gas and equipped with a stirrer tank
The pulverized product 5rt12G- was suspended in anhydrous normal heptane in a 0-round bottom flask, and then αB41 N, N
;N? Add N-tetramethylethylenediamine. The mixture was then left under stirring at room temperature for 45 minutes and then diluted with 300-helbutane to give the catalyst component.

When the solid and liquid in the catalyst component was separated and the T1 content of the solid fraction was measured, it was found to be over 1.02 weight.

2) Polymerization During polymerization, an experiment was carried out in the same manner as in Example 1, except that 120q of triethylaluminum and a511F were used as the catalyst component with T1 atoms, and phenyltriethoxysilane was not used. The results obtained are shown in Table 1.

Table 1

[Brief explanation of the drawing]

(1) FIG. 1 is a schematic drawing to help understand the present invention. (2) OaO (*1) and diester of aromatic dicarboxylic acid (*2) may be allowed to coexist at any time of suspension, contact (1), and contact (2), respectively. (3) OaOn Mg ((4H@O)t of pot 1
It is used at a weight ratio of α5 or more.

Claims (2)

[Claims] (1) Diethoxymagnesium (a) is suspended in an aromatic hydrocarbon (b) that is liquid at room temperature, and then brought into contact with titanium tetrachloride (c). (c) in contact with the suspension and/or
or diester of an aromatic dicarboxylic acid (d) and calcium oxide (e) in any step during contacting
A solid catalyst component for polymerizing olefins obtained by coexisting calcium oxide (e) with diethoxymagnesium (a) in a weight ratio of 0.5 to 1.5. (2) Diethoxymagnesium (a) and calcium oxide (e) are co-pulverized in advance, the resulting pulverized composition is suspended in a liquid aromatic hydrocarbon (b) at room temperature, and then titanium tetrachloride is The product obtained by contacting with (c) is further contacted with titanium tetrachloride (c), and at this time, a diester of an aromatic dicarboxylic acid (d) is allowed to coexist during the suspension and/or contact. Claim No. (1) obtained by
A solid catalyst component for polymerizing olefins as described in .