JPS60139706A - Olefin polymerization catalyst component - Google Patents

Abstract

PURPOSE:The titled high-activity catalyst component, obtained by contacting a dialkoxymagnesium with an aromatic dicarboxylic acid ester, a halohydrocarbon, and a titanium halide. CONSTITUTION:An olefin polymerization catalyst component is obtained by contacting 1pt.wt. dialkoxymagnesium (e.g., diethyoxymagnesium) with about 0.01- 2pts.wt. aromatic dicarboxylic acid mono- (or di-) ester (e.g., dimethyl phthalate), a halogydrocarbon (e.g., carbon tetrachloride) in an amount sufficient to form a suspension and at least about 0.1pt.wt. titanium halide of the formula: TiX4 (wherein X is a halogen), e.g., titanium tetrachloride. This catalyst component and an organoalminum are used as an olefin polymerization catalyst of a high performance. Especially when a polymer of a high MI is produced, this catalyst hardly loses its performances over a long period of time.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a high-performance catalyst component that exhibits high activity when subjected to the polymerization of olefins and is capable of obtaining stereoregular polymers in high yield. This invention relates to a catalyst component for polymerizing olefins obtained by contacting dialkoxymagnesium, mono- and diesters of aromatic dicarboxylic acids, halogenated hydrocarbons, and titanium halides.

Conventionally, as a catalyst for polymerizing olefins, a combination of a solid titanium halide and an organoaluminum compound as a catalyst component is well known and widely used. Since the yield of the polymer (hereinafter referred to as the catalyst component and the polymerization activity of titanium in the catalyst component) is low, a so-called deashing step to remove the catalyst residue has been unavoidable. This demineralization process uses large amounts of alcohol or chelating agents, so
Such recovery equipment or recycling equipment is essential;
There are many problems related to resources, energy, and others, and it is an important issue that those skilled in the art would like to solve as soon as possible. In order to eliminate this complicated deashing step, many studies have been made and proposals have been made to increase the polymerization activity per titanium in the catalyst component, especially in the catalyst component.

In particular, a recent trend is to support transition metal compounds such as titanium chlorides, which are active ingredients, on a carrier material such as magnesium chloride, and when used in the polymerization of olefins, the polymerization activity per titanium in the catalyst component is reduced. There are many proposals that have dramatically improved this.

However, the chlorine contained in magnesium chloride, which is the main carrier material, has the same disadvantage as the halogen element in titanium halides, which has a negative effect on the polymer produced, and for this reason, the effect of chlorine is virtually ignored. However, there remained unresolved issues such as the need to have as high an activity as possible, or the need to keep the concentration of magnesium chloride itself low.

The present invention aims to reduce residual chlorine in the produced polymer while maintaining a high degree of polymerization activity per catalyst component and the yield of a stereoregular polymer.
-200454, we proposed a method for producing a catalyst component for the polymerization of olefins, and achieved the intended purpose.

However, when using the catalyst component using magnesium chloride as a carrier or the catalyst component obtained in the patent application No. 57-2QO454, the polymerization activity per unit time is high at the initial stage of polymerization, but as the polymerization time progresses. The resulting drop is large, causing problems in process operation, and
In cases such as block copolymerization, where it is necessary to make the space between □ longer during polymerization, it is almost impossible to use it practically.

The present inventors have arrived at the present invention as a result of intensive research to solve the problems remaining in the prior art, and hereby propose the present invention.

That is, the feature of the present invention is that (a) dialkoxymagnesium, (b) mono- and diester of aromatic shikanobonic acid, (C) halogenated hydrocarbon, and (
a) General formula T1X4 (in the formula, X is a halogen element)
It is an object of the present invention to provide a catalyst component for polymerizing olefins obtained by contacting a titanium halide represented by (hereinafter sometimes simply referred to as titanium halide).

When olefins are polymerized using the catalyst component obtained according to the present invention, the resulting polymer not only has extremely high w-body regularity, but also has extremely high activity, so that catalyst residues in the resulting polymer are Furthermore, since the amount of residual chlorine is so small as to be 11 [11], the effect of chlorine on the produced polymer can be reduced to such an extent that no deashing step is required at all.

Chlorine contained in the produced polymer not only causes corrosion of equipment used in processes such as granulation and molding, but also causes deterioration and yellowing of the produced polymer itself, and this has been reduced. has extremely important meaning for those skilled in the art.

Furthermore, a feature of the present invention is to provide a catalyst that solves the essential drawback of so-called highly active supported catalysts, in which the activity per unit time of the catalyst component decreases significantly as the polymerization progresses. It's there.

In addition, in the production of industrial olefin polymers, it is common to allow hydrogen to coexist during polymerization from the viewpoint of MI sub-control, but the catalyst component using magnesium chloride as a carrier does not become active in the coexistence of hydrogen. It also had the disadvantage that the stereoregularity was significantly reduced. but,
When olefins are polymerized in the presence of hydrogen using the catalyst component obtained according to the present invention, the MI of the produced polymer is
The activity and stereoregularity hardly decrease even when the ratio is extremely high, and such an effect is of great benefit to those skilled in the art.

To further comment on the effects of the present invention, in the industrial production of olefin polymers, the bulk specific gravity of the produced polymer is a very big problem, but the catalyst component obtained by the present invention is extremely excellent in this respect as well. It shows the characteristics.

The dialkoxymagnesium used in the present invention includes jetoxymagnesium, dibutoxymagnesium, diphenoxymagnesium, dipropoxymagnesium, di-5ee-butoxymagnesium, di-te
Among them, rt-butoxymagnesium, diisopropoxymagnesium and the like are preferred, among which jetoxymagnesium and dipropoxymagnesium are preferred.

The aromatic dicarboxylic acid mono- and diesters used in the present invention are preferably phthalic acid or terephthalic acid mono- and diesters, such as dimethyl phthalate, dimethyl terephthalate, diethyl phthalate,
Diethyl terephthalate, dipropyl phthalate, dipropyl terephthalate-1, dibutyl phthalate, dibutyl terephthalate, diisobutyl phthalate, cyamyl phthalate, diisoamyl phthalate, ethylbutyl phthalate! -, ethyl isobutyl phthalate, ethyl globyl phthalate, etc.

The halogenated hydrocarbon used in the present invention is preferably an aromatic or aliphatic hydrocarbon chloride that is liquid at room temperature, such as propyl chloride, butyl chloride, butyl bromide, propyl iodide, chlorobenzene, benzyl chloride, dichloroethane. , trichloroethylene, dichloropropane, dichlorobenzene, trichlorodichloroethane, chloroform, carbon tetrachloride, and methylene chloride.

Monotanno-halides represented by the general formula T1X4 (wherein X is a halogen element) used in the present invention include TiC1a, TiBr4+ TiI4
Among them, Tic/, 4 is preferable.

When obtaining the catalyst component of the present invention, the use and ratio of each raw material constituting the catalyst component is arbitrary as long as it does not adversely affect the performance of the catalyst component to be produced, and there are no particular restrictions. , usually dialkoxymagnesium 1f, mono and diester of aromatic dicarboxylic acid is 0
．． 01 to 22, preferably in the range of O1 to 1v, and titanium chlorides are in the range of 0.1 or more, preferably 1 g
or less (-) range.

Further, the halogenated hydrocarbons can be used in any proportion, but it is necessary that the proportion is 1:1 so that a suspension can be formed.

At this time, the order and method of contacting the raw materials forming the catalyst component are not particularly limited, but a preferred embodiment is to suspend the component (Al in the component (c) An example of a method is to add a suspension to component (d) and cause a contact reaction, and at some point during the reaction, component (b) is allowed to coexist.

The contact conditions for each raw material in the present invention are: when dialkoxy/magnesium is suspended in a halogenated hydrocarbon, in the presence or absence of mono- and diesters of aromatic dicarboxylic acids, usually from 0°C. It is preferable to maintain suspension at a temperature up to the boiling point of the hydrogenated hydrocarbon for a period of 100 hours or less, preferably 10 hours or less.

In the present invention, the suspension and the titanium halide are brought into contact with each other in the presence or absence of mono- and diesters of aromatic dicarboxylic acids at a temperature ranging from -10°C to the boiling point of the titanium halide used. Range: 10 minutes to 1
It is preferable to carry out the test for 00 hours.

It is also possible to repeatedly contact the composition obtained with the contacting agent with titanium halide, and it is also possible to wash it using an organic solvent such as n-heptane.

These series of operations in the present invention are preferably carried out in the absence of oxygen, moisture, and the like.

The catalyst component produced as described above is combined with an organoaluminum compound to form a catalyst for polymerizing olefins. The aluminum compound used is used in a molar ratio of 1 to 1000, preferably 1 to 300, per mole of titanium atoms in the catalyst component. However, it is not prohibited to add a third component such as an electron-donating substance during polymerization.

Polymerization can be carried out in the presence or absence of an organic solvent, and the strained olefin j,p gas can be used in either gas or liquid state. The polymerization temperature is 200°C or less, preferably 100°C or less, and the polymerization pressure is 100 KP/ca-0 or less, preferably 50 K.
9/Ci・0 or less.

Olefins that can be independently polymerized or copolymerized using the catalyst component of the present invention include ethylene, propylene, and -butene.

The present invention will be explained in detail below using all Examples and Comparative Examples.

Example 1 [Preparation of catalyst component] A container 20 sufficiently purged with nitrogen gas and equipped with a stirrer
Jetoxymagnesium 57 in a 0 me round bottom flask
, dibutyl phthalate 207 and methylene chloride 25
Me was added to create a suspension, and the mixture was stirred under reflux for 1 hour. This suspension was then poured into a volume ff 500 equipped with a stirrer.
T i C14200 at room temperature in a ml round bottom flask.
m1! The mixture was pumped into the reactor, heated to 90°C, and reacted with stirring for 2 hours. After the reaction is complete, add 200 ml of n-hebutane at 40°C.
Wash with Tall 10 times and add new T i C14200.
m1! was added and reacted at 90°C for 2 hours with stirring.

After the reaction was completed, it was cooled to 40°C, and then 20°C of n-heptane was added.
0+m! The cleaning was repeated, and when chlorine was no longer detected in the cleaning solution, the cleaning was completed and the catalyst component was used. At this time, when the solid and liquid in the catalyst component was separated and the titanium content of the solid was measured, it was found to be 361% by weight.

[Overlapping]

Internal volume completely replaced with nitrogen gas2. 700 mef of n-heptane was charged into an autoclave equipped with a stirrer, and triethylaluminum 3 was added while maintaining a nitrogen gas atmosphere.
01 mg, phenyltrinidoxin run (32 m9), and then 03 mg of the catalyst component as titano atoms were charged.

Thereafter, 300 ml of hydrogen gas was charged, the temperature was raised to 70° C., and while propylene gas was introduced, polymerization was carried out for 4 hours while maintaining the pressure of 6 K9 /al·0. After completion of polymerization, the obtained solid polymer was separated into i11, heated to 80° C., and dried under reduced pressure. On the other hand, the weight of the polymer dissolved in the polymerization solvent after condensing the P solution is designated as (3), and the hI of the solid polymer is designated as (B). The solid polymer still obtained was extracted with boiling n-hebutane for 6 hours to obtain the jF polymer, which was insoluble in n-hebutane.
C).

Polymerization activity (1)) per catalyst component is expressed as In addition, the yield of crystalline polymer (■) is expressed by the formula The yield of total crystalline polymer (F5) was determined from the formula.

In addition, residual chlorine in the produced polymer (G), M of the produced polymer
I is represented by (H), and the bulk specific gravity of the produced polymer is represented by (■). The results obtained are as shown in Table 1.

Example 2 An experiment was conducted in the same manner as in Example 1 except that the polymerization time was changed to 6 hours. The results obtained are shown in Table 1.

Example 3 Methylene chloride 50m/! The experiment was conducted in the same manner as in Example 1, except for using the following. Incidentally, the titanium content of the solid fraction at this time was 352% by weight. During polymerization, an experiment was conducted in the same manner as in Example 1.

The results obtained are shown in Table 1.

Example 4 A catalyst component was prepared in the same manner as in Example 1, except that 12-dichloroethane was used instead of methylene chloride. Note that the titanium content of the solid fraction at this time was 366% by weight. During polymerization, an experiment was conducted in the same manner as in Example 1. The results obtained are shown in Table 1.

Example 5 A catalyst component was prepared in the same manner as in Example 1 except that the reaction temperature with TiC44 was 100°C. Note that the titanium content of the solid fraction at this time was 336% by 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 An experiment was conducted in the same manner as in Example 1 except that dipropyl phthalate 152 was used. Note that the titanium content of the solid fraction at this time was 392% by weight.

During polymerization, phenyltriethoxysilane was added to 641
The experiment was conducted in the same manner as in Example 1 except that No. 119 was used. The results obtained are shown in Table 1.

Example 7 Cyamyl phthalate was used instead of dibutyl phthalate.
The experiment was conducted in the same manner as in Example 1, except that 50% of methylene chloride was used. Incidentally, the titanium content of the solid agglomerate at this time was 4.19% by weight. During polymerization, an experiment was conducted in the same manner as in Example 1. The results obtained are shown in Table 1.

Comparative Example 1 [Preparation of catalyst components] □ 2100 f of MgCl and 31.59 g of ethyl benzoate are ground for 18 hours under a nitrogen gas atmosphere. The hindlimb crushed composition 1002 was taken out and the internal volume was reduced to 200 under nitrogen gas atmosphere.
Ti'Ct4500-
was added and the reaction was stirred at 65°C for 2 hours. After the reaction is complete, cool to 40°C, let stand, and decant.
′ Lehi clear fluid was removed. Then 1000 m of n-heptane
g1. ,.

The cleaning solution was repeatedly washed with water, and when no chlorine was detected in the washing solution, the washing was completed and the catalyst was used as a catalyst component.

At this time, when the solid and liquid in the catalyst component was separated and the titanium content of the solid was measured, it was found to be 1.28 weight-1.

[Overlapping]

During polymerization, the catalyst component contains 10 to 10 titanium atoms.
The procedure was carried out in the same manner as in Example 1 except that □ was used. The results obtained are shown in Table 1.

Comparative Example 2" □ [Preparation of catalyst component] Capacity "2" sufficiently purged with nitrogen gas and equipped with a stirrer
A 00'mg round-bottomed flataco was charged with magnesium stearate (5f1), jetoxymagnesium (52%), ethyl benzoate (2.0ml) and methylene chloride (50ml) to form a suspension, and the mixture was stirred under reflux for 1 hour. Next, this suspension/suspension was pumped into TiCt4' 200 me at room temperature in a 500-capacity round bottom flask equipped with a stirrer □.
The mixture was heated to .degree. C. and reacted for 2 hours with stirring. After the reaction was completed, it was washed 10 times with 200°C of n-heptane at 40°C.
TiCt4200- was newly added and the mixture was allowed to react at 6°C for 2 hours with stirring.

After the reaction was completed, it was cooled to 40°C, and then 20°C of n-heptane was added.
01n (!) was repeated, and when chlorine was no longer detected in the cleaning solution, the cleaning was completed and the catalyst component was used. At this time, the solid and liquid in the catalyst component was separated to determine the titanium content in the solid. When measured, it was 383 heavy.

[Overlapping]

During the polymerization, an experiment was carried out in the same manner as in Example 1, except that 137 ml of p-)ethyl ruylate and 05 ml of T1F44 as the catalyst component were used. The results obtained are the first
As shown in the table.

Table 1 Procedural amendment January 31, 1980 Kazuo Wakasugi, Commissioner of the Patent Office1, Indication of the case, Patent Application No. 244-873 of 1982, Title of the invention, Catalyst component for polymerization of olefins3 Amendment. Patent applicant address: 1-26-5 Toranomon, Minato-ku, Tokyo Name: Toho Titanium Co., Ltd. Representative: Tadao Negishi 4th representative: 107 Telephone: 586-8670 Address: 4-3 Akasaka, Minato-ku, Tokyo 1 Kyodo Building Akasaka No. 312) Voluntary 6. “Claims column” and “Detailed explanation of the invention” column of the specification subject to amendment 7. Contents of the amendment 1. Correct the columns as shown in the attached sheet.

2. The Detailed Description of the Invention column in the specification is corrected as follows.

(1) Page 12, line 9 of the specification: [1-1000, preferably 1-300] is replaced with "1-10"
00” and correct it.

(2) Same page 12, line 20; Correct "1-butene, etc." to "1-butene, etc."

(3) Page 13, line 15: Correct "after the reaction ends" to "after the reaction ends."

2. Claims (1) (a) dialkoxymagnesium, (b) mono- and diesters of aromatic dicarboxylic acids, (c) halogenated hydrocarbons, and (d) general formula 'piX4 (in the formula
is a halogen element. ) A catalyst component for polymerizing olefins obtained by contacting a titanium halide represented by:

(2) Component (a) is suspended in component (C), and the resulting suspension is added to component ω) for a contact reaction, at which time component (b) is present in the coexistence. A catalyst component for the polymerization of olefins according to claim (1), which is obtained by the following steps.

(3) The catalyst component for polymerizing olefins according to claim (1) or (2), wherein the dialkoxymagnesium is jetoxymagnesium or dipropoxymagnesium.

(4) The catalyst component for polymerizing olefins according to claim (1) or (2), wherein the aromatic dicarboxylic acid mono- and diesters are phthalic acid or terephthalic acid mono- and diesters.

(5) The mono- and diesters of phthalic acid or terephthalic acid are dimethyl phthalate, dimethyl terephthalate, diethyl phthalate, diethyl terephthalate, dipropyl phthalate, dipropyl terephthalate, dibutyl phthalate, dibutyl terephthalate, diimbutyl phthalate, cyamyl phthalate, The catalyst component for polymerizing olefins according to claim (4), which is isoamyl phthalate, ethyl butyl phthalate, ethyl isobutyl phthalate, or ethyl propyl phthalate.

(6) The catalyst component for polymerizing olefins according to claim (1) or (2), wherein the halogenated hydrocarbon is a chloride of an aromatic aliphatic hydrocarbon that is liquid at room temperature. .

(7) Claim (1) or Claim 1, wherein the --logenated hydrocarbon is chlorobenzene, benzyl chloride, propyl chloride, butyl chloride, dichloroethane, trichloroethane, carbon tetrachloride, chloroform, or methylene chloride. (2) The catalyst component for polymerizing olefins as described in item (2).

(8) The halogenated hydrocarbon is propylchloro±J
1. The catalyst component for polymerizing olefins according to claim (1) or (2), which is dichloroethane, chloroform, carbon tetrachloride, and methylene chloride.

(9) The catalyst component for polymerizing olefins according to claim (1) or (2), wherein the titanium halide is TiCl2.

01 The olefins are ethylene, propylene and 1
-butene, and is used in the homopolymerization or copolymerization of these catalyst components for olefin polymerization according to claim (1).

Claims (9)

[Claims] (1) (a) dialkoxymagnesium, (b) mono- and diesters of aromatic dicarboxylic acids, (C) halogenated hydrocarbons, and (d) general formula T1X4 (wherein XF
i) It is a rogen element. ) A catalyst component for the polymerization of olefins obtained by contacting a titanium chloride represented by: (2) Component (al) is suspended in component (cl), and the resulting suspension is added to component (d) for a contact reaction, at which time component (b) is allowed to coexist at some point. A catalyst component for the polymerization of olefins according to claim (1), which is particularly obtained. (3) The dial according to claim 1 or 2, wherein the dialkoxymagnesium is jetoxymagnesium or dialkoxymagnesium.
A sick tongue is attached to a sickle. (4) The catalyst component for polymerizing olefins according to claim (1) or (2), wherein the aromatic dicarboxylic acid mono- and diesters are phthalic acid or terephthalic acid mono- and diesters. (5) The mono- and diester of phthalic acid or terephthalic acid is dimethyl phthalate, dimethyl terephthalate, diethyl phthalate, diethyl terephthalate,
Jig mouth, pyru phthalate, diethyl terephthalate, dibutyl phthalate, diethyl terephthalate, diisobutyl phthalate~1, cyamyl phthalate, diynamyl phthalate, ethyl butyl phthalate, ethyl isobutyl phthalate v-), lta ethyl butyl phthalate catalyst. component. (6) For the polymerization of olefins according to claim 1 or 2, wherein the logenated hydrocarbon is a chloride of an aromatic or aliphatic hydrocarbon that is liquid at room temperature. Catalyst component.・ (7) Claim (1), wherein the halogenated hydrocarbon is chlorobenzene, benzyl chloride, propyl chloride, butyl chloride, dichloroethane, trichloroethane, carbon tetrachloride, chloroform, or methylene chloride. Or the catalyst component for polymerizing olefins as described in item (2). (8) The halogenated hydrocarbon is propyl chloride,
Claims (1) or (2) which are dichloroethane, chloroform, carbon tetrachloride and methylene chloride
) Catalyst component for polymerizing olefins as described in item 1. (9) The catalyst component for polymerizing olefins according to claim (1) or (2), wherein the titanium halide is TiCl4. The catalyst component for polymerizing olefins according to claim (1), wherein the olefins are ethylene, propylene, and j-butene, and the catalyst component is used for homopolymerization or copolymerization of these olefins.