JPH02232206A - Catalyst for polymerization of olefin - Google Patents

Abstract

PURPOSE:To make it possible to form a catalyst which can exhibit high activity in the polymerization of an olefin and can give a polymer having a uniform shape and a high stereoregularity by combining a solid catalyst component containing titanium with an epoxy-p-menthane compound and an organoaluminum compound. CONSTITUTION:This catalyst for the polymerization of an olefin is formed by combining a solid catalyst component (I) obtained by grinding a substance obtained by reacting a metallic magnesium powder with at most 2mol, per mol of this powder, of an alkyl halide compound in the presence of iodine and a tetraalkoxytitanium, successively adding a tetraalkoxytitanium, an aliphatic alcohol and a phthalic diester to the obtained product at 100 deg.C or above in the presence of an aliphatic hydrocarbon to treat the product with each of them, and adding titanium tetrachloride to the obtained product to treat the product with it; an epoxy-p-menthane compound (II); and an organoaluminum compound (III).

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a high-performance catalyst that acts with high activity and is capable of obtaining well-shaped and highly stereoregular polymer pairs when used in the polymerization of olefins. It is. More specifically, the present invention provides a catalyst for polymerizing olefins, which is comprised of a special solid catalyst component +1), an epoxyparamenthane compound 11), and an organoaluminum compound (8), as will be detailed later. . [Prior Art] Recently, in place of the conventionally well-known titanium trichloride catalyst component as a solid catalyst component in catalysts for polymerizing olefins such as propylene, a new type of catalyst component has been developed in which titanium, which is an active component, is electrolyzed into magnesium chloride. Many products have been developed and provided that are supported together with a donor. 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-pulverized product of acid ester and magnesium chloride treated with titanium tetrachloride. [Problems to be Solved by the Invention] However, when these are used in combination with organoaluminum compounds to industrially carry out the polymerization of olefins, especially the stereoregular polymerization of propylene, l-butene, etc., it is difficult to carry out the polymerization reaction. It is essential to use an organic monocarboxylic acid ester as an electron donor, and in this case, it is necessary to use an extremely large amount of the organic monocarboxylic acid ester, which imparts a characteristic ester odor to the resulting polymer. There was a problem with that. Furthermore, although these catalysts have high activity at the initial stage of polymerization, their deactivation over time causes problems in process simulation, and when the polymerization time is longer, such as in block copolymerization, it is practically impossible to use them. was impossible. In order to improve this point, JP-A-54-94590 discloses that a catalyst component is prepared using magnesium dihalide as a starting material, and organic aluminum compounds, organic carboxylic acid esters, and compounds having 0-R groups, etc. A method is disclosed in which the combination is used for the polymerization of olefins, 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 organic carboxylic acid ester contained in the catalyst is treated with a titanium halide or washed with an organic solvent.
The amount is such that the odor problem of the produced polymer can be ignored. However, as mentioned above, the amount of organic carboxylic acid ester used during 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 it is produced. At present, it is contained in the polymer, and therefore, it can be said that 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 catalyst obtained is not sufficient for practical use in terms of performance and sustainability of activity. The reality is that this cannot be said. [Means for Solving the Problems] In order to solve the various problems in the prior art as described above, the present inventors conducted intensive research and found that the present invention has resulted in a polymer changeover having a high degree of stereoregularity. We succeeded in providing a high-performance catalyst that can That is, the present invention comprises the following solid catalyst component [I], the following epoxyparamenthane compound [I1], and the following (
The present invention provides a catalyst for polymerizing olefins, characterized in that it is made of the organoaluminum compound of the present invention. TI) Substance (a) obtained by reacting metallic magnesium powder with at least twice the mole of alkyl monohalide in the presence of iodine and tetraalkoxytitanium (b) are ground, and the resulting product is aliphatic. Tetraalkoxytitanium (h) at 100°C or higher in the presence of a hydrocarbon (c),
Aliphatic alcohol (d) and phthalic acid diester (e)
A solid catalyst component obtained by adding titanium tetrachloride <f> to the obtained product and further processing; [1] Consisting of an epoxy paratantan compound and ■ an organoaluminum compound. The present invention provides a catalyst for polymerizing olefins. The catalyst for polymerizing olefins of the present invention will be explained in more detail below. First, the solid catalyst component (I) will be explained. In order to obtain the substance obtained by reacting the metal magnesium powder and the alkyl monohalide in the above (a) in the presence of iodine (hereinafter simply referred to as the substance (a)), commercially available metal magnesium powder and the alkyl monohalide are used. is reacted in the absence of an organic solvent and in the presence of iodine,
At this time, it is necessary to use 2 or more moles of the alkyl monohalide per 1 mole of the metal magnesium powder. In addition, the reaction temperature and reaction time are arbitrary as long as the above reaction proceeds sufficiently, and are not particularly limited.
It 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 IR spectrum of the substance (a) obtained by the 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, etc. Examples include chloride, isobutyl chloride, benzyl chloride, hexyl chloride and octyl chloride. Tetraalkoxytitanium of (b) (hereinafter simply referred to as (1)
) As the alkoxy group, an alkoxy group having 1 to 10 carbon atoms is used, and an alkoxy group having 3 or 4 carbon atoms is particularly preferably used. One type or two or more types of tetraalkoxytitanium can be used. (b) The amount of substance used is usually (a) Substance 1. The total amount is in the range of 0.1 to 10 g. The aliphatic hydrocarbon (c) (hereinafter simply referred to as (c) substance) and the aliphatic alcohol (d) (hereinafter simply referred to as (c))
d) substances) are all liquid at -30°C to 50°C. (c) Preferable examples of the substance include aliphatic hydrocarbons having 5 to 12 carbon atoms, such as pentane, hexane, hebutane,
Preferred examples of the substance (d) include aliphatic alcohols having 2 to 10 carbon atoms, such as ethanol, propanol, butanol, pentanol, hexanol, and Examples include ctanols and their isomers. The phthalic acid diesters (hereinafter simply referred to as (e) substances) mentioned above include dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dibrobyl phthalate, dibutyl phthalate, diisobutyl phthalate, diamyl phthalate, diisoamyl phthalate, and ethyl phthalate. Examples include butyl phthalate, ethyl isobutyl phthalate and ethyl brobyl phthalate. The above substance (e) is used in a ratio of 0.1 d or more, preferably 0.2 to 1.0 rn1, per 1 g of the substance (a). Titanium tetrachloride (f) used in the present invention is (a)
It is used in a proportion of 1 g or more, preferably 5 g or more per 1 g of the substance. The contact temperature at this time is usually D°C or higher and 130°C or lower. The contact time is at least 10 minutes, preferably at least 30 minutes. The obtained solid catalyst component m is mixed with n-hebutane, l as necessary.
- You may wash using an organic solvent such as toluene, or
It may be treated repeatedly with titanium tetrachloride (f). All of these aspects are included in one aspect of implementing the present invention. A series of simulations related to the preparation of the solid catalyst component in [1] above in the present invention are carried out in the absence of oxygen, moisture, and the like. The solid catalyst component [I] prepared as described above is prepared as described above.

[Functions and effects of the invention]

When the catalyst for olefin polymerization according to the present invention is used to polymerize olefins, it exhibits an unprecedentedly high activity, so that the amount of catalyst residue present in the resulting polymer is extremely reduced. In addition, 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. In addition, according to the catalyst of the present invention, by not adding an organic carboxylic acid ester during polymerization, it is possible to solve the major problem of adhesion of ester odor to the produced polymer. Furthermore, conventionally, there has been a common drawback in so-called highly active supported catalysts that the activity per unit time of the catalyst decreases significantly as the polymerization progresses, but in the catalyst according to the present invention, The decrease in activity with the passage of polymerization time is extremely small compared to conventionally known catalysts, so it is useful when polymerization times are longer, such as in copolymerization, and higher polymerization pressures are used. Since the increase in activity is large in this case, 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 well-shaped structure and a high degree of stereoregularity can be obtained. Furthermore, in the production of industrial olefin polymers, it is common to allow hydrogen to coexist during polymerization from the viewpoint of Ml control. These catalysts had the disadvantage that their activity and stereoregularity were significantly reduced in the presence of hydrogen. However, when polymerizing olefins in the presence of hydrogen using the catalyst according to the present invention,
Even when the Ml of the resulting polymer is very high, the activity and stereoregularity do not decrease. Such an effect was strongly desired by those skilled in the art. 9. It does not produce undesirable fine powder polymers in the polyolefin manufacturing process, is suitable for gas-phase polymerization, which has been attracting attention recently, and has excellent fluidity, so it is suitable for so-called post-polymerization treatments such as bomb transportation and centrifugation. In addition to making the process easier,
Since the particle shape is excellent, the granulation process can be omitted, and various other effects can be achieved. [Example] Below, the present invention will be explained in more detail with reference to Examples. Example 1 (1) (a) Preparation of the substances Capacity 2. equipped with a stirrer. Oj! Using a round-bottomed flask, the flask was sufficiently purged with nitrogen gas, and then 30 g of metal magnesium powder, 1.0 g of iodine, and 1.0 g of n-butyl liquid were added. 2 1! was charged and reacted for 5 hours at the boiling point of n-butyl chloride. After the reaction was completed, the supernatant liquid was removed, and the product was washed three times with 500-n-butyl chloride, and then dried and smoked under reduced pressure to obtain a powdery substance. (2) Preparation of solid catalyst component 30 g of the powdered material obtained in (1) above and tetrabutoxytitanium2. 0- in a nitrogen gas atmosphere, 25 mm
Capacity 1 filled with 4/5 of the total volume of stainless steel poles of φ
．． Charge the OIl into a vibrating mill pot and set the vibration frequency to 1 4 3.
It was ground for 17 hours at 0v, p,m and a shaking width of 3.5mm. In a round bottom flask with a capacity of 500 rnl equipped with a stirrer, 10 g of the above pulverized product, 75 m7' of n-decane, and 10 ml of tetrabutoxytitanium were charged under a nitrogen gas atmosphere, and the temperature was raised to 125°C and the mixture was stirred for 1 hour. I processed the time. Next, a solution containing 25 volumes of n-hebutane and 6.8 volumes of 2-ethylhexyl alcohol was added dropwise to the mixture over a period of 30 minutes, and the mixture was reacted for 1 hour while maintaining the temperature at 125°C. After that, it was cooled to 70°C, and 25rr of n-hebutane was added! A mixed solution of l. The resulting product was washed 5 times with 200 mj2 of hebutane, then 75 ml of TIC14
was added and reacted at 115°C for 3 hours. After the reaction 2
A solid catalyst component was obtained by washing 10 times with 00d of hebutane. At this time, the titanium content in the solid catalyst component was measured and found to be 4.72% by weight. (3) Polymerization of brobylene Using a small crepe with a stirrer and an internal volume of 2.0 liters, after completely replacing it with nitrogen gas, 200 mg of triethylaluminum and 70 mg of 1,3 epoxy parathane were added.
and the solid catalyst component 3. 0 mg was charged. Then hydrogen gas l. 8, f2, liquefied propylene 1
．． 41 was charged, and a polymerization reaction was carried out at 70°C for 1 hour. After the polymerization reaction is completed, the produced polymer is dried under reduced pressure at 80°C, and the amount of the obtained product is defined as (A>. Also, this product is extracted with boiling 1!f! n-heptane for 6 hours to convert it to n- A polymer insoluble in butane is obtained, and the amount of this is designated as (B). The polymerization activity (c) per solid catalyst component used is expressed by the following formula. Examples except that the polymerization time was 30 minutes. An experiment was conducted in the same manner as in Example 1. The results obtained are shown in Table 1. Example 3 Same as Example 1 except that the same amount of dibrobyl phthalate was used instead of dibutyl phthalate. The experiment was conducted with a titanium content of 4.5% in the solid catalyst component.
It was 88% by weight. The polymerization was carried out in the same manner as in Example 1. I did this. The results obtained are shown in Table 1. Further, the yield (0) of the total crystalline polymer is expressed by the following formula. Further, the amount of residual chlorine in the produced polymer is expressed as (B), and the MI of the produced polymer is expressed as (F), and the obtained results are shown in Table 1. Example 2 Table ■

[Brief explanation of the drawing]

FIG. 1 is a schematic drawing to help understand the present invention. Patent applicant: Toho Chi, Tanium Co., Ltd. Procedural amendment (method) October 3, 1999

Claims (1)

[Claims] 1) (I) After pulverizing the substance (a) obtained by reacting metal magnesium powder with at least twice the mole of alkyl monohalide in the presence of iodine and tetraalkoxytitanium (b). , Tetraalkoxytitanium (b), aliphatic alcohol (d) and phthalic acid diester (e) are sequentially added to the obtained product in the presence of an aliphatic hydrocarbon (c) at 100°C or higher for treatment. , a solid catalyst component obtained by adding titanium tetrachloride (f) to the obtained product and further processing; an olefin characterized by comprising (II) an epoxyparatantan compound and (III) an organoaluminum compound Catalyst for polymerization.