JPS6225110A - Catalyst component for polymerizing olefin and catalyst - Google Patents

Abstract

PURPOSE:The titled catalyst, obtained by using a component prepared by bringing a specific metallic compound into contact with a magnesium compound, aromatic dicarboxylic acid diester and halogenated hydrocarbon and titanium compound and an organoaluminum compound in combination and useful for highly stereoregular polymerization. CONSTITUTION:A catalyst for polymerization obtained by using (A) a component prepared by bringing (i) an alkoxy compound of an element of Group III in the periodic table into contact with (ii) a dialkoxymagnesium (iii) an aromatic dicarboxylic acid diester and (iv) a titanium compound expressed by the formula TiX4 (X is halogen) and (B) a silicon compound expressed by the formula (R is H, alkyl or aryl; R' is alkyl or aryl; 0<=m<=4) and (C) an organoaluminum compound in combination.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is a high-performance polymer that is highly active during the polymerization of olefins and can obtain stereoregular polymers in extremely high yields. Regarding the catalyst fraction and the catalyst, more specifically, it is obtained by contacting an alkoxy compound of an element of Group I of the periodic table, dialkoxymagnesium, a diester of an aromatic dicarbonate, a halogenated hydrocarbon, and a titanium halide. The present invention relates to a catalyst component for polymerizing olefins and a catalyst for polymerizing olefins comprising the catalyst component, a silicon compound, and an organoaluminium compound.

[Conventional technology]

Conventionally, as a highly active catalyst for polymerizing olefins, a combination of a solid titanium logide and an organoaluminum compound as a catalyst component is well known and widely used. Since the yield of the titanium/υO polymer (hereinafter referred to as the catalyst component and the polymerization activity per titanium in the catalyst component) is low, a so-called deashing step to remove the catalyst residue has been unavoidable. Since this deashing process uses a large amount of alcohol or chelating agent, recovery equipment or regeneration equipment for these is indispensable, and there are many problems associated with resources, energy, etc., and those skilled in the art would like to solve them as soon as possible. This was an important issue. In order to eliminate this complicated deashing process, many studies have been made and proposals have been made to increase the Ox 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 halides, which are active ingredients, on carrier materials such as magnesium chloride, and when used in the polymerization of olefins, the polymerization activity of titanium in the catalyst component can be dramatically increased. There are many proposals to raise the standard.

[Problem that the invention seeks to solve]

However, chlorine contained in magnesium chloride, which is the main carrier material, has the disadvantage of having an adverse effect on the produced polymer, similar to the halogen element in titanium halides.

This left unresolved issues, such as requiring high activity to the extent that the effects of chlorine could be virtually ignored, and the need to keep the concentration of magnesium chloride itself low.

The present inventors have determined that while maintaining the polymerization activity of the catalyst component and the yield of the stereoregular polymer at a high level, the O
For the purpose of reducing residual chlorine, JP-A-59-
In 91107VC, we proposed a method for producing a catalyst component for polymerizing olefins, and achieved our initial objective.

However, when using a catalyst component using magnesium chloride as a carrier, or a catalyst component obtained in JP-A-59-91107, the 901 activity per unit time is high at the initial stage of polymerization, but decreases as the polymerization time progresses. In addition to causing problems in process operation, it is necessary to lengthen the polymerization time for block copolymerization, etc. In some cases,
It was almost impossible to use it practically.

The present inventors, as a result of intensive research, have proposed the present invention in order to solve the problems remaining in the prior art and further improve the quality of the produced polymer.

[Means for solving problems]

That is, the features of the present invention are as follows: (A) (a) 7i: elemental alkokene compound of group m of the periodic table, (b) dialkoxymagnesium, (C) aromatic dicarboxylic diester, (( Co., Ltd.), and (8) a titanium halide represented by the general formula TiX4 (in the formula, X is a halogen element). (B) General formula 5IRH1(OR
') a-rn (wherein RFi Mizuki is an alkyl group or an aryl group, R' is an alkyl group or an aryl group, and m is 0≦m≦4. It is sometimes called a silicon compound.]
and (C) A catalyst component for polymerizing olefins, characterized in that it is used in combination with an organoaluminum compound, and (7,) (a) an alkoxy compound of an element in group m of the periodic table, (b) dialkoxymagnesium, (C) diester of aromatic dicarboxylic acid, (d) halogen (hydrogen monide, and (@) titanium halide represented by the general formula T1X4 (wherein X is a halogen element) (hereinafter referred to as
It is sometimes simply called titanium halide. (B) General formula BiRm(OR')4-m (wherein R is hydrogen, an alkyl group or an aryl group, R' is an alkyl group or an aryl group, and m (0≦m≦4.

As the alkoxy compound of Group I of the periodic table used in the present invention, an alkoxy compound of aluminum is preferable.

The dialkoxymagnesium used in the present invention includes jetoxymagnesium, dibutoxymagnesium, diphenoxymagnesium, dipropoxymagnesium, di-5ea-butoxymagnesium, di-ta
Examples include rt-putoymagnesium and diisoproboxymagnesium, among which jetoxymagnesium and dipropoxymagnesium are preferred.

The diester of aromatic dicarboxylic acid used in the present invention is preferably a diester of phthalic acid or terephthalic acid, such as dimethyl phthalate, dimethyl terephthalate, diethyl phthalate, diethyl tere-7-thaleate, diethyl phthalate, siglobil-tere-7-thale,
Examples include dibutyl phthalate, dibutyl terephthalate, cyanobutyl phthalate, cyamyl phthalate, diynamyl phthalate, ethyl butyl phthalate, ethyl isobutyl phthalate, and ethyl butyl phthalate.

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 bromide, butyl bromide, propyl iodide, 0-dichlorobenzene, benzyl Examples include chloride, dichloroethane, trichloroethylene, dichloropropane, dichlorobenzene, trichloroethane, carbon tetrachloride, chloroform, methylene chloride, among others, 0-dichlorobenzene, propyl chloride, dichloroethane, chloroform, tetrachloride. Carbon and methylene chloride are preferred.

General formula TiX4 used in the present invention (wherein X
is a halogen element. ) titanium/% C
llNon-components include Ti (t4, TiBr4,
Examples include Tix4, among which Ti(]t4 is preferred.

The silicon compound used in the present invention is:
Examples include phenylalkoxysilane and alkylalkoxysilane. Examples of phenyl alkoxysilanes include tosite, phenyltrimethoxysilane, phenyltriethoxy 7rane, phenyltripropoxy 7rane, phenyltriine globoxy 7rane, diphenyldimethoxysilane, diphenyljethoxy 7rane, etc. Examples of alcoholic compounds include tetramethoxysilane, tetraethoxysilane, trimethoxyethylsilane, trimethoxymethylsilane, triethoxymethylsilane, ethyltriethoxysilane, and ethyltriisopropoxysilane. can.

The organoaluminum compounds used in the present invention include trial aluminum, dialkyl aluminum halides, alkyl aluminum cibarides, and mixtures thereof.

When obtaining the catalyst component in the present invention, the usage ratio of each raw material, contact conditions, etc. are arbitrary as long as they do not adversely affect the performance of the catalyst component to be produced, and are not particularly limited. The diester of aromatic dicarboxylic acid has an α of 01 to 2 da, preferably 11 to 1 f, and the titanium halide has an α of 1 f or more for a total of 1 of the alkoxy compounds of Group 1 elements and dialkoxy7 magnesium. , preferably in the range of 1 or more. Further, the halogenated hydrocarbon can be used in any proportion, but it is preferably in an amount that can form a suspension.

At this time, the order and method of contacting the raw materials forming the catalyst component are not particularly limited, but in the first embodiment, an alkoxy compound of an element in group m of the periodic table and dialkoxymagnesium were ground. The resulting composition is then contacted with a diester of an aromatic dicardyl and a titanium halide in the presence of a halogenated hydrocarbon, or, in a second embodiment, an alkoxy of an element of Group I of the Periodic Table. The composition obtained after grinding the compound, dialkoxy7magnesium and diester of aromatic dicarboxylic acid is treated with titanium chloride in the presence of a halogenated hydrocarbon.
Preferably, contact is made with a halogenide.

The pulverization of the alkoxy compound of the element of group m of the periodic table and dialkoxymagnesium in the first aspect is as follows:
This is usually carried out for 5 minutes or more using a ball mill, a vibration mill, etc., and the resulting composition is brought into contact with the diester of aromatic dicarboxylic acid and the titanium halide in the presence of a hydrogenated hydrocarbon, usually from 0°C. The process is carried out for 5 minutes to 100 hours at a temperature up to the boiling point of the titanium halide used.

In the 20th aspect, the alkoxy compound of the element of group m of the periodic table, the dialkoxy7 magnesium, and the diester of aromatic dicarboxylic acid are usually pulverized for 5 minutes or more using a ball mill, a vibration mill, etc. The contact between the titanium halide and the titanium halide is carried out in the presence of a hydrogenated hydrocarbon at a temperature ranging from 0° C. to the boiling point of the titanium halide used for 5 minutes to 100 hours.

It is also possible to contact the composition obtained after contacting each component constituting the catalyst with a titanium halide, and it is also possible to wash it using an organic solvent such as n-hebutane. It is possible.

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 has broad peaks around 20=32° and around 50° in its X-ray spectrum, and when combined with the silicon compound and organoaluminum compound, it can be used as a catalyst for polymerizing olefins. Form.

The organoaluminum compound used is used in a simole ratio of 1 to 1000 per mole of titanium atoms in the catalyst component, and the silicon compound has a simole ratio of 1 or less, preferably 1005 to Q , 5c?
Used in range.

The polymerization can be carried out in the presence or absence of an organic solvent, and the olefin monomer 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 F'
1100 Yu/c1n”・G or less, preferably 50 kp/
α2·G or less.

Olefins to be homopolymerized or copolymerized using the catalyst component of the present invention include ethylene, propylene, 1-butene, and the like.

〔Effect of the invention〕

When olefins are polymerized using the catalyst components and catalysts obtained according to the present invention, the resulting polymer not only has extremely high stereoregularity but also has extremely high activity. The amount of residual chlorine can be kept extremely low, and the amount of residual chlorine is almost negligible, so there is no need for a deashing process at all. It can be virtually eliminated.

Chlorine contained in the produced polymer causes corrosion of 1:FK equipment used in processes such as granulation and molding, and also causes deterioration and yellowing of the produced polymer itself. It was extremely impressive for those skilled in the art to be able to do this! It has important meaning.

Furthermore, the present invention is characterized in that the activity of the catalyst component per unit time decreases significantly as the polymerization progresses.
The objective is to solve the essential drawbacks of so-called highly active supported catalysts and to provide a catalyst that can be practically applied not only to homopolymerization but also to copolymerization.

In addition, in the production of industrial olefin polymers, t″i
, hydrogen at the time of gold? Although it is common to coexist with hydrogen from the viewpoint of M engineering control, etc., the catalyst component using magnesium chloride as a carrier has the disadvantage that its activity and stereoregularity are significantly reduced in the coexistence of hydrogen. Ta. However, when olefins are polymerized in the presence of hydrogen using the catalyst component and catalyst obtained by the present invention,
Even when the C)M content of the resulting polymer is very high, the activity and stereoregularity hardly decrease, and this effect is of great benefit to those skilled in the art.

〔Example〕

The present invention will be specifically explained below using examples.

Example 1 [Catalyst components! 4! J-trining grobokiku aluminum 5f and diethoxymagnecum A5f were heated to 25 mφ in a nitrogen gas atmosphere.
After filling the stainless steel pole to its full capacity, the next capacity is 1.0t.
placed in a vibrating mill pot with a vibration frequency of 1430 v, p,
Grinding treatment was carried out at room temperature for 1 hour using a shaker and a shaker. Into a round bottom flask with a capacity of 500 d and fully purged with nitrogen gas and equipped with a stirrer A, 55 t of the composition obtained by the pulverization process and 15 d of 0-dichlorobenzene were added, and 1.8 d of dibutyl phthalate was added under stirring. - and Ti
O4200df was added, the temperature was raised to 110°C, and the reaction was carried out with stirring for 2 hours. After the reaction was completed, it was washed 10 times with butane 200d at 40°C, washed once at 40°C with TiC64200d, and further washed with τ1ct420.
0d was added, and the mixture was reacted at 110° 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.
Repeated cleaning at 0 sd was performed, and when chlorine was no longer detected in the cleaning solution, the cleaning was completed and the catalyst component was removed. 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 2.89 by weight.

[Overlapping]

Internal volume completely replaced with nitrogen gas2. Charge n-hebutane 700- to an OL autoclave with a stirring device,
Triethyl aluminum 30 while maintaining nitrogen gas atmosphere
1 Hg, phenyl trieth, and then the catalyst component was charged as a titanium atom to 13 Cape. Thereafter, 120@t of hydrogen gas was charged, the temperature was raised to 70°C, and while propylene gas was introduced, 9/-.GO positive pressure was maintained at 6' to carry out polymerization for 4 hours. After the polymerization was completed, the obtained solid polymer was separated, heated to 80° C., and dried under reduced pressure. On the other hand F
The amount of polymer dissolved in the polymerization solvent after condensing the liquid is (A), and the amount of solid polymer is (B). Further, the obtained solid polymer was extracted with boiling n-hebutane for 6 hours to obtain a polymer insoluble in n-hebutane, and this amount was designated as (C).

The polymerization activity Φ) of each catalyst component was expressed by the formula and the yield of the crystalline polymer (F, ) was expressed by the formula, and the yield of the total crystalline polymer ('F) was determined from the formula. Also, residual chlorine in the produced polymer? (G), the MI of the produced polymer (expressed in units). The results obtained are shown in Table 1.

Example 2 The polymerization time was 6 hours, and the catalyst component was titanium atoms [
The experiment was conducted in the same manner as in Example 1 except that 12 capes were charged. The results obtained are as shown in Table 1.

Example 5 Example 1 except that 1.52 dipropyl phthalate was used.
An experiment was conducted in the same manner. Incidentally, the titanium content in the solid content at this time was 2.97% by weight. During the polymerization, an experiment was conducted in the same manner as in Example 1, except that 70q of phenyltriethyl chrysanthemum 7ran was used. The results obtained are shown in Table 1.

Example 4 Triisopropoxyaluminum sr, jetoxymagnesium 45? and dipropyl 7 thale) 15f were crushed in the same manner as in Example 1.

The obtained composition 62 was fully replaced with 1 clt of nitrogen gas and placed in a 500-capacity round bottom flask equipped with a stirrer, and 0-dichlorobenzene 15- and TiO4200a were added.
j was charged, the temperature was raised to 110°C, and the reaction was carried out with stirring for 2 hours. After the reaction was completed, it was washed 10 times with 200 d of butane at 40°C, and then washed with fresh K TiC4200 for 40 ml.
After cleaning once at 90°C, T1C1,200- was further added and the mixture was stirred and reacted at 90°C for 2 hours. After the reaction was completed, the mixture was cooled to 40° C., and washed with 20 times more n-hebutane repeatedly. When chlorine was no longer detected in the washing solution, the washing was completed, and a catalyst component was obtained. Incidentally, the titanium content F'i in the solid content at this time was 2.91 weight ik.

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

The resulting formulations are shown in Table 1.

Claims (5)

[Claims] (1) (A) (a) an alkoxy compound of an element of Group III of the periodic table, (b) dialkoxymagnesium, (c) a diester of an aromatic dicarboxylic acid, (d) a halogenated hydrocarbon, and (e) Obtained by contacting a titanium halide represented by the general formula TiX_4 (wherein X is a halogen element), (B) general formula SiR_m(OR')_4_-_m (wherein R is hydrogen, an alkyl group or an aryl group, R' is an alkyl group or an aryl group, and m is 0≦m
≦4. ) A catalyst component for polymerizing olefins, which is used in combination with a silicon compound represented by (C) and an organoaluminum compound. (2) After grinding components (a) and (b), the resulting composition is mixed with components (c) and (e) in the presence of component (d).
) A catalyst component for polymerizing olefins according to claim (1), which is obtained by contacting with a catalyst component. (3) After crushing components (a), (b) and (c),
The catalyst component for polymerizing olefins according to claim (1), which is obtained by contacting the resulting composition with component (e) in the presence of component (d). (4) (A) (a) an alkoxy compound of an element of group III of the periodic table, (b) dialkoxymagnesium, (c) a diester of an aromatic dicarboxylic acid, (d) a halogenated hydrocarbon, and (e) A catalyst component obtained by contacting a titanium halide represented by the general formula TiX_4 (wherein X is a halogen element); (B) General formula SiR_m(OR')_4_-_m (wherein R is hydrogen, alkyl or aryl group, R' is an alkyl group or aryl group, and m is 0≦m≦4); and (C) an organoaluminum compound. (5) After the catalyst component mills components (a) and (b), the resulting composition is mixed with component (a) and (b) in the presence of component (d).
c) and (e) or component (a).
, (b) and (c) and then contacting the resulting composition with component (e) in the presence of component (d). Polymerization catalyst.