JPH01161003A - Solid catalyst component and catalyst for polymerizing olefin - Google Patents

Abstract

PURPOSE:To produce the subject component which acts with high activity, and gives a stereoregular polymer in a high yield, by reacting diethoxymagnesium, titanium tetrachloride, a tetraalkoxytitanium, and phthaloyl dichloride in a specified manner. CONSTITUTION:Diethoxymagnesium (a) is suspended in an alkylbenzene (b), and is brought into contact with titanium tetrachloride (c) with the volume ratio of (c) to (b) of 1 or below. A tetraalkoxytitanium (d) is added to it at 80 deg.C or below, and phthaloyl dichloride (e) is added to it at 80-135 deg.C thereby reacting them to produce a solid product. The solid product is washed with the alkylbenzene (b). The solid product is reacted with titanium tetrachloride (c) in the presence of the alkylbenzene (b) with the volume ratio of (c) to (b) of 1 or below, thereby producing the aimed solid catalyst component.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a high-performance solid that exhibits high activity when subjected to the polymerization of olefins and can yield stereoregular polymers in high yield. This invention relates to a catalyst component and a catalyst for polymerizing olefins using the same.

[Conventional technology and its problems]

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 polymer (hereinafter referred to as the catalyst component and the polymerization activity of titanium in the catalyst component) is low, a demineralization step is unavoidable in order to remove catalyst residue. Since a large amount of alcohol or 7'2-H chelating agent is used in this deashing process, a recovery device or a regeneration device is indispensable, and there are many resource, energy, and other problems involved, and it is difficult for those skilled in the art to is an important issue that requires immediate resolution.

In order to eliminate this complicated deashing process, many studies have been made and proposals have been made to increase the polymerization activity of the catalyst component, especially titanium (equivalent to titanium) in the catalyst component.

In particular, a recent trend is to support transition metal compounds such as titanium halides, which are active ingredients, on carrier materials such as magnesium chloride, and when used in the polymerization of olefins, the polymerization activity per titanium in the catalyst component can be dramatically increased. I've seen many suggestions for increasing it.

However, it has the disadvantage that the chlorine contained in magnesium chloride, which mainly contains magnesium chloride as a carrier material, has a negative effect on the produced polymer, similar to the halogen element in titanium halides. There are still some unresolved issues, such as the need for high activity so that the influence of superchlorine can be ignored, and the need to keep the concentration of magnesium chloride itself low.

In addition, when polymerizing olefins, especially stereoregular polymerization of propylene, 1-butene, etc., is carried out industrially, it is common to coexist an electron-donating compound such as an aromatic carboxylic acid ester in the polymerization system. It is essential in catalysts that use a catalyst component containing magnesium as a carrier in combination with an organoaluminium compound. However, this aromatic carboxylic acid ester imparts a characteristic ester odor to the resulting polymer, and removal of this has become a major problem in the industry.

Furthermore, so-called highly active supported catalysts, such as catalysts using catalyst components with magnesium chloride as a carrier, have high activity at the initial stage of polymerization, but are largely deactivated, which poses problems in process operation, and can cause blockages. In cases such as copolymerization, where it is necessary to extend the polymerization time, it is almost impossible to use it practically. In order to improve this point, for example, in JP-A-54-94590, a catalyst component is prepared using magnesium dihalide as a starting material,
Organoaluminide metal, organic carboxylic acid ester, M
A method for polymerizing olefins in combination with a compound having a -0-R group 'Th has been shown, but since an organic carboxylic acid ester is used during polymerization, the problem of odor of the resulting polymer has not been solved. Moreover, as can be seen from the examples in the same publication, it requires very complicated operations, and it cannot be said that practically sufficient results have been obtained in terms of performance and duration of activity.

On the other hand, various solid catalyst components for polymerizing olefins or solid catalyst components comprising dialkoxymagnesium, titanium tetrachloride, and an electron-donating compound have already been developed and proposed.

For example, in JP-A-55-152710, it was discovered that in order to obtain high catalyst activity, a large amount of an organoaluminum compound must be used during polymerization, and that in order to control the molecules 2 of the produced polymer, The purpose of this is to improve the drawback that stereoregularity of the resulting polymer decreases when hydrogen is added to the dialkoxymagnesium obtained by a specific operation with a halogenated hydrocarbon and a donor-donating compound. A method for obtaining a catalyst component by contacting with a tetravalent titanium halide in the presence of is disclosed.

Analysis from Example 2 specifically exemplifying this method reveals that dialkoxymagnesium is suspended in carbon tetrachloride,
Ethyl benzoate and titanium tetrachloride were added at 5°C to form a suspension 'f! Stirring is carried out for 2 hours while maintaining a temperature of about 5°C. The resulting nine solid components were isolated, washed five times with in-octane, suspended in titanium tetrachloride at 80°C, stirred for 2 hours, and then washed five times with in-octane to remove the solid catalyst component. I am getting .

The proportion of this solid catalyst component used in combination with triethylaluminum as a catalyst for polymerization of olefins is shown as Example 1.

However, the solid catalyst component prepared by the method disclosed in JP-A-55-152710 has sufficient polymerization activity, stereoregular polymer yield, and activity sustainability when used in olefin polymerization. This cannot be said to indicate performance.

Therefore, in order to solve this problem, the present inventors added a diester of dialkoxymagnesium and an aromatic dicarboxylic acid to a halogenated hydrocarbon in JP-A-61-108611! We have developed a catalyst for polymerizing olefins consisting of a solid catalyst component, a piperidine derivative, and an organoaluminum compound obtained by treating the suspension in a cloudy state, and then adding the suspension to a titanium halide and reacting it. We succeeded in obtaining excellent specific characteristics in terms of durability.

However, this catalyst still leaves room for further improvement in the stereoregularity and bulk specific gravity of the produced polymer.

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

[Means for solving problems]

That is, the feature of the present invention is that after suspending jetoxymagnesium (a)' in alkylbenzene (b), titanium tetrachloride (C ), then add tetraalkoxytitanium (a) at 80°C or below, and then add 1 ft. of phthalic acid dichloride (e) at a temperature range of 80°C to 135°C, and the solid material obtained by reacting. Separated and washed with alkylbenzene, the solid material is reacted with titanium tetrachloride (c) in a volume ratio of 1 or less to the alkylbenzene (b) in the presence of a niary alkylbenzene (b). Characterized solid catalyst component for polymerizing olefins and the solid catalyst component, and the general formula 191Rm(OR')4-m (wherein Ri is a group selected from an alkyl group, an chloroalkyl group, an aryl group, or a vinyl group) , m R may be a combination of different groups and are R/u alkyl groups.

When R is an alkyl group, the alkyl group may be the same as or different from R'. mtzO≦m≦3. An object of the present invention is to provide a catalyst for polymerizing olefins, which is characterized by comprising a silicon compound and an organoaluminum compound represented by the following formulas.

The tetraalkoxytitanium used in the preparation of the solid catalyst component of the present invention includes tetrabutoxytitanium,
Tetraisobutoquikutitanium, Tetrapropoquikutitanium,
Examples include tetraisobutokykutitanium.

The alkylbenzenes (b) used to suspend the shed magnesium (a) in the preparation of the solid catalyst component of the present invention include toluene, xynon, ethylbenzene, flobylbenzene, trimethylbenzene, etc. It will be done.

Tetraalkoxytitanium (a) and phthalic acid dichloride (
Jetoxymagnesium (a) t to the usage ratio of e)
For o y (in the range of LO1 to α5-.
Titanium tetrachloride cc > rs jetoxymagnesium (a)
1 for to t. Of or more, and the capacity ratio to alkylbenzene (b) is 1 or less. Note that it is necessary to use the alkylbenzene (b) in an amount that can form a suspension of jetoxymagnesium (a).

The solid catalyst component of the present invention is jetoxymagnesium (a)
f alkylbenzene (1)) and then brought into contact with titanium tetrachloride (c) at a volume ratio of 1 or less to the alkylbenzene (1)), and then tetraalkoxytitanium (d) is added at 80°C or less. and then further heat to 80℃~1'
A solid substance obtained by adding and reacting phthalic acid dichloride (e) in a temperature range of 55°C is washed with alkylbenzene, and the solid substance is further added with a volume ratio of 1 to the alkylbenzene value) in the presence of an alkylbenzene value). It is obtained by the following titanium tetrachloride (a) f reaction, but at this time, the reaction in the temperature range of 80 to 135°C is usually 10
The duration ranges from minutes to 10 hours. The alkylbenzene value used in the above washing may be the same as or different from the alkylbenzene ('b). There are no particular limitations on the temperature during cleaning. Examples of alkylbenzenes used for cleaning include those listed in the exemplification of alkylbenzenes described above.

Note that, prior to washing with this alkylbenzene, it is possible to perform washing with an organic solvent other than the alkylbenzene.

Next, the solid material after this washing is further treated with the alkylbenzene (t) in the presence of the alkylbenzene (Cb).
1) with titanium tetrachloride (c) in a volume ratio of 1 or less.

The temperature at this time is not particularly limited, but is preferably in the range of 60°C to 135°C, and this reaction is usually carried out at 1
The duration ranges from 0 minutes to 10 hours. Suitable temperature ranges for each of the above reactions are appropriately determined depending on the type of alkylbenzene used.

The above reaction is usually carried out under stirring using a container equipped with a stirrer.

Shedokiku magnesium (a) alkylbenzene (b)
Although it is not particularly necessary to carry out the suspension in ) at around room temperature, it is preferable because it is easy to operate and can be carried out using a simple device.

The solid catalyst component thus obtained can be used as n-
It is also possible to wash with an organic solvent such as hebutane. This solid catalyst component can be used as a catalyst for polymerization of olefins either as it is after washing or after being dried after washing.

Next, the catalyst for oretin polymerization of the present invention using the above solid catalyst component will be explained.

-maximum 1 of the above @) used in the catalyst of the present invention
31Rm(OR')4-m (in the formula, R is a group selected from an alkyl group, a cycloalkyl group, an aryl group, or a vinyl group, m R's may be a combination of different groups, R
Pa is an alkyl group. When R is an alkyl group, the alkyl group may be the same as or different from R'. m20≦m≦3. ) and L-r can be phenylalkoxysilane, alkylalkoxysilane, phenylalkylalkoxysilane, fluoroalkylalkoxysilane, cycloalkylalkylalkoxysilane, and the like. Furthermore, as a series of phenylalkoxy 7ranes, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, phenyltriisopropoxysilane, diphenyldimethoxy 7rane, diphenylshedkiku 7rane, etc. can be mentioned, and alkylalkoxysilane Examples include tetramethoxy 7-ran, tetraethoxysilane, trimethoxyethyl 7-ran, trimethoxymethylsilane, triethoxymethyl 7-ran, ethyltriethquinsilane, ethyltriisoglopoquicuran, and the like.

The organoaluminum compound (C) used in the catalyst of the present invention includes trialkylaluminum,
Mention may be made of dialkyl aluminum rhamnolides, alkyl aluminum sinolides, and mixtures thereof.

The organoaluminum compound (C) used in the catalyst of the present invention has a molar ratio of 1 to 1000 per mole of titanium atoms in the solid catalyst component (D), and the silicon compound (E) It is used in a molar ratio per mole (LO1 to Q, 5).

Polymerization can be carried out in the presence or absence of an organic solvent, and the monomer can be used in either gas or liquid state. Polymerization temperature 122
The temperature is 00°C or lower, preferably 100°C or lower, and the polymerization pressure is 100kli/1-In/G or lower, preferably 50°C or lower.
Yu/α1・G or less.

In homopolymerization using the catalyst according to the present invention, the olefins to be copolymerized include ethylene, propylene, 1-7'thene,
4-methyl-1-pentene and the like.

〔Effect of the invention〕

When olefins are polymerized using the catalyst for olefin polymerization according to the present invention, the resulting polymer has extremely high stereoregularity.

! i9. In the industrial production of polyolefins, the bulk specific gravity of the produced polymer is a very big problem due to the capacity of the polymerization equipment, the capacity of the post-treatment process, etc., but the catalyst according to the present invention also has problems in this respect. It has extremely excellent properties.

Furthermore, the titanium tetrachloride used in the preparation of the solid catalyst component of the present invention is characterized in that it is used in an extremely small amount compared to conventional techniques. Titanium tetrachloride reacts with oxygen and moisture in the air to form hydrochloric acid gas, emitting white smoke and a strong irritating odor, making it difficult to handle.It is possible to reduce the amount used and reduce costs. It also offers significant benefits in the production of solid catalyst components, such as reduced yield, ease of operation, and prevention of pollution sources.

Furthermore, since the catalyst according to the present invention exhibits a high activity that could not previously be expected, the amount of catalyst residue present in the produced polymer can be kept extremely low, and therefore the amount of residual chlorine in the produced polymer can also be reduced by deashing. It can be reduced to the extent that no process is required at all.

In addition, according to the catalyst of the present invention, by not adding organic carboxylic acid esters or nitrogen compounds during the preparation of the solid catalyst component and the non-polymerization using the solid catalyst component, the major problem of odor adhesion to the resulting polymer can be avoided. can be completely resolved.

Furthermore, conventionally, there is a common drawback in so-called high-activity supported catalysts in 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 decrease in activity with the passage of polymerization time is extremely small compared to conventionally known catalysts, it is extremely useful in cases where the polymerization time is longer, such as in copolymerization.

Furthermore, in the production of industrial olefin polymers, it is common to allow hydrogen to coexist during polymerization from the viewpoint of suppressing M production. Nine catalysts using esters had the disadvantage that their activity and stereoregularity were 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. This effect has been strongly desired by those skilled in the art.

〔Example〕

The present invention will be specifically explained below with reference to examples.

Example 1 [Preparation of solid catalyst component] A container sufficiently purged with nitrogen gas and equipped with a stirrer, t5
00- round bottom flask, jetoxymagnesium 10
? and toluene 60- to form a suspension, and then to this suspension T i Ot.

In addition to 40d1, the temperature was raised to 70°C, and tetrabutoxytitanium t5-1 was added.The temperature was further raised to 90°C, and phthaloyl dichloride 2.0- was added. Thereafter, the temperature was raised to 115°C and the mixture was reacted with stirring for 2 hours.

After the reaction was completed, it was washed twice with 200- toluene at 90°C, and 60- toluene and 440- TiC were newly added.
The reaction was allowed to proceed at 5°C for 2 hours with stirring. After the reaction was completed, the reaction product was washed 10 times with 200°C of n-heptane at 40°C. The titanium content in the solid catalyst component thus obtained was measured to be 2.72% by weight.

[Overlapping]

Internal volume 2. Triethyl aluminum 20019 in an autoclave with an OL stirring device. 45 my of 7 runs of diphenyl dimethoxychloride and 2 aoq of the solid catalyst component were charged. Then hydrogen gas 1.8A.

1.41 f of liquefied propylene was charged, and polymerization was carried out at 70°C for 30 minutes. After polymerization, the obtained polymer was heated to 80°C.
Dry under reduced pressure and use the obtained amount as c). This product was extracted with boiling n-hebutane for 6 hours to obtain a polymer insoluble in n-hebutane, and this amount was designated as (B).

The polymerization activity (C)) per solid catalyst component used and the yield Φ of the total crystalline polymer are expressed by the formula (III) (D) = -X 100 (% false).

Further, the amount of residual chlorine in the produced polymer is expressed as (F), the M concentration of the produced polymer is expressed as (F), and the bulk specific gravity k (C1). The expected results are shown in Table 1.

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

Example 5 Toluene at 100-1T i C! An experiment was conducted in the same manner as in Example 1 except that 40-t.

The titanium content in the obtained solid catalyst component was 2.6
I got caught in the 1st weight class. During polymerization, experiments were conducted in the same manner as in Example 1. The results obtained are shown in Table 1.

Example 4 Implementation 9 in addition to 2.0 durability for tetrabutoxy titanium 1
The experiment was conducted in the same manner as 'lJ1. Incidentally, the titanium content d in the obtained solid catalyst component was 2.99 weight. During polymerization, experiments were carried out in the same manner as in Example 19. The results obtained are shown in Table 1.

Example 5 An experiment was conducted in the same manner as in Example 1, except that xylene according to the same method was used instead of toluene. The titanium content in the obtained solid catalyst component was 2.80% by weight. The polymerization was conducted in the same manner as in Example 1. The results obtained are shown in Table 1.

Table 1

[Brief explanation of the drawing]

FIG. 1 is a schematic drawing to help understand the present invention. Patent Applicant Toho Titanium Co., Ltd. Procedural Amendment September 9, 1988 Director General of the Japan Patent Office Yoshi 1) Tsuyoshi Moon 1, Indication of Case Patent Application No. 517324 of 1988 Title of Invention Solid Catalyst Component for Polymerization of Olefins and relationship with the Catalyst 5 Amendment Case Patent Applicant Address: 1081 (458)-44N 2-13-31 Konan, Minato-ku, Tokyo Name: Toho Titanium Co., Ltd. Representative Shun Yashima - 1-Yu 4. Date of amendment order Table 1 on page 22 of the specification of the invention is corrected as shown in the attached sheet. Table 1

Claims (2)

[Claims] (1) Diethoxymagnesium (a) is suspended in alkylbenzene (b) and then the alkylbenzene (b)
Contact with titanium tetrachloride (c) at a volume ratio of 1 or less to titanium tetrachloride (d) at 80°C or less.
The solid substance obtained by adding and reacting phthalic acid dichloride (e) at a temperature range of 80°C to 135°C is washed with alkylbenzene, and the solid substance is further washed with alkylbenzene to remove the presence of alkylbenzene (b). A solid catalyst component for polymerizing olefins, which is obtained by reacting titanium tetrachloride (c) with a volume ratio of 1 or less to the alkylbenzene (b) as described below. (2) (A) Diethoxymagnesium (a) is suspended in alkylbenzene (b) and then brought into contact with titanium tetrachloride (c) in a volume ratio of 1 or less to the alkylbenzene (b), and then 80°C or less The solid substance obtained by adding tetraalkoxytitanium (d) and reacting by adding phthalic acid dichloride at a temperature range of 80°C to 135°C is washed with alkylbenzene, and the solid substance is further added with alkylbenzene ( A solid catalyst component for polymerizing olefins, characterized in that it is obtained by reacting the following titanium tetrachloride (c) in the presence of b) at a volume ratio to the alkylbenzene: (B) General formula SiR_m(OR') _4_-_m (wherein R is a group selected from an alkyl group, a cycloalkyl group, an aryl group, or a vinyl group, m R's may be a combination of different groups, and R' is an alkyl group. In the case of an alkyl group, the alkyl group may be the same as or different from R' (m is 0≦m≦3) and (C) an organoaluminum compound. A catalyst for polymerizing olefins characterized by the following.