KR790001204B1 - Manufacturing method of ethylene - Google Patents

Abstract

Ethylene was low-pressure polymorized with a new catalyst which was synthesized by the reaction of (i) aluminium-magnesium organic soluble complex, AlnMgmR13nR22n (R1,R2 = C1-10 hydrocarbonyl group ; n,m>o, m/n=0.1-10), (ii) organic nonsoluble products obtained by the reaction of Ti or V compd. contg. halogen atom, with organic aluminium compds. A1R3pH3-p(R3 = C1-20 hydrocarbyl group, 2 <=p<3).

Description

Polymerization Method of Ethylene

The present invention relates to a process for polymerizing ethylene and copolymerizing ethylene with other α-olefins. More specifically, the present invention relates to a novel low pressure polymerization method of ethylene by a novel catalyst synthesized using an organoaluminium-magnesium complex.

In the low pressure production of polyethylene using a catalyst composed of a transition metal compound belonging to group IV-VIA of the periodic table and an organometallic compound of group I-III of the periodic table, numerous catalysts have been developed and developed under the discovery of K. Ziegler. However, most catalyst systems do not have sufficient activity and require a process for removing the catalyst from the polymer produced, and the cost of the catalyst is high.

In recent years, the development of a high activity catalyst aiming at reducing the cost of a catalyst while omitting this catalyst removal step and simplifying the process has been actively conducted.

Highly active catalysts are roughly classified into two types. That is, a catalyst system using a combination of a so-called catalyst catalyst obtained as a Ziegler-based catalyst synthesis carrier on a solid surface and a solid component obtained by reducing a titanium or vanadium compound from a specific organometallic compound with a specific organometallic activator. to be.

It is known that many catalysts using halides, hydroxyhalides, alkoxides or organic acid salts of magnesium as carrier components exhibit particularly high activity (for example, Japanese Patent Publication Nos. 1968-13,050 and 1972-42,137). And 1972-42,039 and Japanese Patent Laid-Open No. 1972-5941).

In addition, in a combination system of a specific organometallic compound and a transition metal compound, a catalyst using a solid component prepared by a reaction of a Greenian reagent or an RMgOR compound and a transition metal compound synthesized in an inert medium (for example, Japanese patent) Japanese Patent Application Laid-Open No. 1972-40,959, Japanese Patent Laid-Open No. 1971-4,391), a catalyst using a solid component obtained by reacting a specific organoaluminum compound with a titanium compound (for example, JP-A No. 1972-26,380) or titanium; Catalysts using solid components including vanadium compounds (for example, JP-A No. 1972-28,708 and 28,709) and the like are known as high activity catalysts.

These catalysts can satisfy the activity of the transition metal sugar, but the activity of the solid component sugar is not sufficient, and if the catalyst removal step is omitted completely, problems such as deterioration of the polymer due to halogen residue in the polymer and corrosion of the manufacturing apparatus are caused. It is not solved.

The inventors of the present invention have conducted extensive and thorough studies on catalysts having a high activity to a unit amount of a solid component. Thus, a specific solid component prepared by reacting a specific organoaluminium-magnesium complex with a titanium or vanadium compound is used as an organic aluminum compound. It has been found that a surprisingly high activity catalyst is obtained by combining with.

P＜3의 수이다〕로 표시되는 유기 알미늄 화합물과 반응시켜 얻어진 촉매를 사용하여 에틸렌 또는 에틸렌과 다른 올레핀을 중합시키는 방법에 관한 것이다.Namely, the present invention provides the following formula [A] (i) General Formula Al _n Mg _m R ¹ _3n R ² _2m [wherein R ¹ and R ² represent the same or different carbon atoms having 1-10 carbon atoms, n and m Is a number greater than 0, and m / n is 0.1-10] by reaction of a hydrocarbon-soluble complex compound containing Al and Mg with (ii) a titanium or vanadium compound containing at least one halogen atom. The resulting hydrocarbon-insoluble reaction product is represented by the following formula (B). General Formula ³ AIR ³ _P H _3-P [wherein, R ³ is a hydrocarbon group having 1-20 carbon atoms, and may be the same or different, and P is 2

A method of polymerizing ethylene or other olefins with ethylene using a catalyst obtained by reacting with an organic aluminum compound represented by P &lt;

The organoaluminium-magnesium complex represented by the general formula Al _n Mg _m R ¹ _{3 n} R ^{2 2} _m as one component of the catalyst according to the present invention is already known (West German Publication No. 2,232,685), and the complex and titanium tetrachloride Polymerization of olefins and dienes using catalysts is also known in the publication.

Furthermore, the polymerization of olefins and dienes using catalysts constituting the electrocomplex and titanium tetrachloride has been published in the cited publication. However, the catalysts of this combination do not exhibit very high activity which is insufficient in activity and indeed industrially sought per transition metal solid catalyst component as described above.

In the case of using the two components of the above-cited publication, it is 1/4 or less than the activity of the invention.

The present invention succeeds in obtaining remarkable high activity by reacting a special solid catalyst component obtained by reacting this special organic aluminum-magnesium complex with a titanium or vanadium compound under specific conditions with a specific organic aluminum compound.

When the ethylene polymerization is carried out for the activity per solid component of this catalyst, 30,000 g / g solid catalyst time, ethylene pressure kg / cm 2 or more is possible, which is far higher than any reported value of known catalysts.

Patents of well-known high activity catalysts, for example, Japanese Patent Publication Nos. 1972-42,137, 1972-42,039, and 1972-40,959, all have a value of 2,000-5,000, and only one has 10,000. It is only.

As such, the performance of the catalyst of the present invention that cannot be achieved using conventional catalysts is surprisingly unpredictable, and the superiority of the catalyst of the present invention is obvious.

In the production method using the catalyst according to the present invention, the production of polyethylene having an industrially preferable molecular weight is easy by using a molecular weight regulator such as hydrogen.

The organoaluminium-magnesium complex [component (i)] of the general formula Al _n Mg _m R ¹ _{3 n} R ² _{2 m} used for the synthesis of the catalyst according to the present invention will be described. This complex is a soluble complex in an inert hydrocarbon solvent synthesized by reacting an organoaluminum represented by the general formula AIR ¹ ₃ with an organomagnesium represented by the general formula MgR ² ₂ or R ² MgX (X is halogen). Publication 2,232,685 and ANNALEN Der science 605,93 (1957).

Although the structure of the electric complex is not clear, the complex of R ² Mg is insoluble in a hydrocarbon solvent is soluble in the solvent, and a complex composed of an aluminum component and a magnesium component has been formed, and is believed to be a single complex or a complex mixture. .

In addition, it can also be described by an empirical formula of (AlR ¹ ₃ ) _n (MgR ² ₂ ) _m from the viewpoint of the synthetic component, and it is considered that the hydrocarbon groups bonded to aluminum and magnesium are mutually causing an exchange reaction.

The hydrocarbon group having ¹ to 10 carbon atoms represented by R ¹ in the general formula is an alkyl group, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, amyl and hexyl , Octyl or decyl groups are used well.

Moreover, the hydrocarbon group of 1-10 carbon atoms represented by general formula R <^2> is an alkyl group or an aryl group, and a methyl, ethyl, n-propyl, n-butyl, amyl, hexyl, octyl, or phenyl group is a suitable group.

m and n are numbers greater than 0, and the ratio m / n of magnesium to aluminum is 0.1-10, preferably 0.5-6.

Titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, ethoxytitanium trichloride, propoxytitanium trichloride as the second component, the titanium or vanadium compound containing at least one halogen atom [component (ii)] Halides of titanium or vanadium, such as butyric trimethoxy, dibutoxy trichloride, tributoxy titanium chloride, vanadium trichloride, vanadium trichloride, monobutoxy vanadate dichloride, dibutoxy vanadil chloride, oxy Halides, alkoxyhalides alone or mixtures are used.

The reaction of the organoaluminium-magnesium complex with the titanium or vanadium compound is important for demonstrating the effects of the present invention. The reaction may be carried out at temperatures up to 100 ° C. in an inert reaction medium, for example aliphatic hydrocarbons such as hexane or heptane, aromatic hydrocarbons such as benzene, toluene or xylene, alicyclic hydrocarbons such as cyclohexane or methylcyclohexane, Even better, it is carried out at a temperature of 50 ° C or less.

The reaction ratio of the two catalyst components is recommended because of the high activity in the range of 0.05 to 50 moles, particularly preferably 0.2 to 10 moles, of the organic aluminum-magnesium complex to 1 mole of the titanium or vanadium compound.

The number of moles of the organic aluminum-magnesium complex is used in the total amount of gram molecules of the aluminum and magnesium components.

For example, the AlMg ₆ (C ₂ H ₅ ) ₃ (nC ₄ H ₉ ) ₁₂ complex has 7 moles of 945 g corresponding to the molecular weight of this structural formula.

The hydrocarbon-insoluble reaction product obtained by the reaction can be used as it is if the reaction is completed, but in order to increase the reproducibility of the polymerization, it is preferable to separate from the reaction solution.

As the organoaluminum compound which is another component of the catalyst of the present invention, an organoaluminum compound represented by the general formula AIR ³ _P H ₃ -P is used alone or as a mixture. The hydrocarbon group having 1-20 carbon atoms represented by R ³ in the formula includes an aliphatic hydrocarbon, an aromatic hydrocarbon, and an alicyclic hydrocarbon.

Specific examples of these compounds include dialkyl aluminum hydrides such as diethyl aluminum hydride, di-n-propyl aluminum hydride, diisobutyl aluminum hydride and di-n-butyl aluminum hydride dihexyl aluminum hydride. Rydes and mixtures of their dialkyl aluminum hydrides with trialkyl aluminums are recommended.

The reaction of the catalysts [A] and [B] of the present invention may be carried out simultaneously with the progress of the polymerization under the polymerization conditions by adding both catalyst components in the polymerization system, and may be performed before the polymerization in advance.

In addition, the reaction ratio of the catalyst component is preferably performed in the range of 1 to 3,000 mmol with respect to 1 g of the component [A].

As the polymerization method, conventional suspension polymerization and solution polymerization are possible, and the catalyst may be a polymerization solvent, for example, an aliphatic hydrocarbon such as hexane or heptane, an aromatic hydrocarbon such as benzene, toluene or xylene, or a cyclohexane, methylcyclohexane such as The polymerization may be performed at a temperature of room temperature to 150 ° C. by introducing into the reactor together with the alicyclic hydrocarbon and injecting ethylene at 1-20 kg / cm 2 under an inert atmosphere.

Moreover, in order to adjust the molecular weight of a polymer, it is also possible to add hydrogen, a halogenated hydrocarbon, or the organometallic compound which is easy to cause chain transfer.

Moreover, it is also possible to superpose | polymerize ethylene in the coexistence with monoolefins, such as propylene, butene-1, hexene-1, using the catalyst of this invention.

The principle and practice of the present invention according to the following examples in more detail.

In the Examples, the molecular weight (Mw) was obtained according to the formula (η) = 6.9 x 10 ^-4 Mw ^0.67 (see Journal of Polymer Science 36, 91 (1959)), and the catalyst efficiency was 1 g of a solid component and 1 hour of ethylene pressure in kg. Polymer production amount g / cm <2>.

Example 1

13.8 g of di-n-butyl magnesium and 1.9 g of triethylaluminum were added together with 200 ml of n-heptane in a 500 ml flask and then reacted at 80 ° C. for 2 hours to prepare AlMg ₆ (C ₂ H ₅ ) ₃ (nC ₄ An organoaluminium-magnesium complex of H ₉ ) ₁₂ is synthesized. 80 ml of n-heptane solution containing 40m mol (5.4 g) of the complex and 80 ml of n-heptane containing 40m Mol of titanium tetrachloride were leveled in a flask of 300 ml in which water and oxygen were removed by dry nitrogen substitution. The mixture was stirred at -20 ° C for 4 hours. The resulting hydrocarbon insoluble solid is isolated, washed in n-heptane and 10.6 g of solid is obtained.

5 mg of this hydrocarbon-insoluble solid reaction product and 1.5 m mol of diisobutylaluminum hydride are degassed in a vacuum with 3 L of n-heptane dehydrated and placed in a 5 L autoclave substituted with nitrogen. The internal temperature of the autoclave is maintained at 85 ° C., hydrogen 2.0 kg / cm 2 is pressurized to the gauge pressure, and ethylene is continuously added to the gauge pressure to 6.0 kg / cm 2. By replenishing ethylene, polymerization was carried out for 1 hour while maintaining the voltage at a gauge pressure of 6.0 kg / cm 2 to obtain 605 g of polymer. The molecular weight of the polymer is 6,900 and the catalyst efficiency is 30,300 g / g solid component. time. Ethylene pressure kg / cm 2.

Example 2-6

The same polymerization as in Example (1) using 5 mg of a hydrocarbon-insoluble solid synthesized in the same manner as in Example (1) using the synthetic ingredients and synthesis conditions shown in Table 1 and an organoaluminum component shown in the table as a catalyst The polymerization was carried out under the conditions to obtain the results as shown in the table. The organoaluminium-magnesium complex used here is synthesize | combined by reaction of di-n-butyl magnesium and trialkyl aluminum using the method similar to Example (1).

TABLE 1

Claims (1)

[A] (i) General Formula Al _n Mg _m R ¹ _3n R ² _2m [wherein R ¹ and R ² may be the same or different and each represent a hydrocarbon group having 1-10 carbon atoms, n and m Is a number greater than 0, m / n is 0.1-10] by reaction with a hydrocarbon-soluble complex containing aluminum and magnesium, and (ii) a titanium or vanadium compound containing at least one halogen atom. The resulting hydrocarbon-insoluble reaction product may be the same as or different from [B] in the general formula AIR ³ _P H ₃ -P where R ³ is a hydrocarbon group having 1-20 carbon atoms, and P is 2

A method of polymerizing ethylene or another olefin using a catalyst obtained by reacting with an organoaluminum compound represented by P <3.