KR790001205B1 - Manufacturing method of ethylene - Google Patents

Abstract

Polyethylene and its olefin deriv. were manufd. in the presence of a catalyst prepd. by treating organo A1 compds. with complex compds. soluble in hydrocarbon. The A1 compds. of the general formula (A1R5nX3-n) [R5 = hydrocarbon radical having carbon atom of 1-20, X = selected radical from hydrogen, halogen, alkoxy, allyloxy or siloxy radical, n = 1-3 were prepd. by reacting linear or cyclic siloxane compds. with Ti or Vd compds. containing at least 1>= halogen atom or complex containing organo magnecium.

Description

Ethylene Polymerization Method

The present invention relates to a process for the polymerization of ethylene and the copolymerization of ethylene with other olefins. More specifically, the present invention relates to a novel low pressure polymerization method of olefins by a catalyst synthesized using a novel organomagnesium compound.

A process for the polymerization of polyethylene using a catalyst composed of an organomagnesium compound and a transition metal compound is already known from K. Ziegler's patent (Japanese Patent Office 32-1546). However, the organomagnesium compound itself is not effectively used because it is insoluble in the inert hydrocarbon medium used for catalytic synthesis and polymerization, and obtaining high activity has not been successful.

As a catalyst which solubilizes and effectively uses an organomagnesium compound and increases its activity, for example, an organoaluminum magnesium halide (so-called Grania reagent) of a long chain alkyl group, a complex of a Grania reagent and an ether, or an organic magnesium It is known to use alkoxides (Japanese Patent Publication No. 47-40959, Japanese Patent Application No. 46-19274, etc.). These catalysts are highly active against transition metals, but have the ability to completely omit the catalyst removal step of the polyethylene manufacturing process. As a catalyst which has, it is inadequate in terms of remaining halogen.

The present inventors have used a complex of organomagnesium, organoaluminum and zinc as a catalyst to improve this point, completed a catalyst having extremely high activity for a solid component, and has already applied for a patent. As a result of further studies on this catalyst system, it was found that the catalyst comprising one component of the reactant of the organomagnesium complex and the siloxane compound as a high-performance polymer with excellent properties gave the present invention.

[식 중 R³, R⁴는 수소 또는 탄소원자수 1-10의 탄화수소기를 표시한다〕인 구성단위를 가지는 쇄상 또는 환상의 실옥산 화합물과의 반응물을, (3) 적어도 1개의 할로겐 원자를 함유하는 티탄 또는 바나듐 화합물과 반응에 의하여 생성하는 탄화수소 불용성 반응생성물과, 〔B〕일반식 AIR⁵ _nX_3-n〔식 중 R⁵는탄소원자수 1-20의 탄화수소기, X는 수소, 할로겐, 알콕시, 아릴옥시 또는 실옥시기로부터 선택된 기이며, n은 1-3의 수이다〕로 표시되는 유기알미늄 화합물을 반응시켜 얻은 촉매를 사용하여 에틸렌 또는 에틸렌과 다른 올레핀을 중합하는 방법에 관한 것이다.That is, in the present invention, (A) (1) general formula MαMgβR ¹ mαR ₂ ² β [wherein M is Al or Zn atom, m represents valence of M and R ¹ and R ² are the same or different A hydrocarbon-soluble complex containing an organic magnesium represented by hydrogen or a hydrocarbon group of 1-16 carbon atoms, wherein α and β are numbers greater than 0, and β / α are 0.5-10; and (2) General formula

A reaction product with a chain or cyclic siloxane compound having a structural unit in which R ³ and R ⁴ represents hydrogen or a hydrocarbon group having 1 to 10 carbon atoms is selected from (3) at least one halogen atom. A hydrocarbon insoluble reaction product produced by reaction with a titanium or vanadium compound, and (B) general formula AIR ⁵ _n X _3-n [ _wherein R ⁵ is a hydrocarbon group of 1-20 carbon atoms, X is hydrogen, halogen, alkoxy And an aryloxy or siloxy group, n is a number of 1 to 3]. The present invention relates to a method for polymerizing ethylene or ethylene with other olefins using a catalyst obtained by reacting an organoaluminum compound.

The effect of the catalyst of the present invention is firstly obtained a polymer suitable for the use of injection molding with a narrow molecular weight distribution. Secondly, molecular weight can be easily adjusted and polyethylene can be produced at low hydrogen partial pressure. Thirdly, such useful polymers can be prepared using extremely good catalysts.

The above effects of the present invention will be described in the following examples. The MI used in these examples indicates a Melt Index and was measured using a temperature of 190 ° C. and a load of 2.16 kg according to ASTM D-1238, and R was measured at a load of 21.6 kg under MI measurement conditions. Expressed as a value divided by MI. This value is a measure of the molecular weight distribution, which indicates that the lower the molecular weight distribution is.

Polyethylene for injection molding needs to have MI of 2-10 and R of 25-33. When organoaluminium-magnesium or organozinc-magnesium complexes before reaction with siloxane are used, the value of R is around 45 and cannot be used for injection molding.

In contrast, in the case of using the siloxane reactant of the present invention, R becomes a low value around 30, and moreover, it is possible to control a suitable molecular weight at a hydrogen concentration of 30%. As such, the catalyst of the present invention can impart a polymer for injection molding at a relatively low hydrogen concentration.

As is clear from the examples, the catalyst of the present invention has extremely good efficiency. This high catalytic efficiency indicates that titanium or vanadium atoms are effectively used in the form of a substantially high activity in the present invention.

The catalyst efficiency of the present invention can be 20,000 or more by using 1 g of solid component, 1 hour of polymerization time and 1 kg / cm 2 of ethylene pressure. On the other hand, the efficiency shown by the Example of the above-mentioned patent is 10,000 or less. In this way, the residual amount of halogen in the polymer produced by the method of the present invention is extremely low and it is possible to substantially omit this removal step.

[A] component of the catalyst of the present invention will be described.

Compound [Component (1)] represented by the general formula MαMgβR ¹ mαR ₂ ² β [M, m, R ¹ , R ² , α, β are the meanings of the foregoing] is disclosed in West German Patent Application Publication No. 2232685 and Atomic Nos. 49-47512 and As described above in Atomic No. 49-38377, it is an organoaluminium-magnesium and an organozinc-magnesium complex soluble in a hydrocarbon solvent.

The complex reacts with an organoaluminum compound represented by AlR ¹ ₃ or AlR ¹ ₂ H or an organozinc compound represented by ZnR ¹ ₂ and an organomagnesium compound represented by MgR ² ₂ or R ² MgX (X is halogen). Synthesis according to In the above formula, the hydrocarbon group of 1-16 carbon atoms represented by R ¹ is hydrogen or an alkyl group, and examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, amyl, hexyl, octyl, The decyl is used for good.

Moreover, the hydrocarbon group of 1-16 carbon atoms represented by R ² is an alkyl or aryl group, and a methyl, ethyl, propyl, butyl, amyl, hexyl, octyl or phenyl group is a suitable group. The ratio β / α of aluminum or zinc to magnesium is 0.5-10, preferably 1-6. Hereinafter, the complex thereof is referred to as an organomagnesium complex.

인 구성단위를 가지는 실옥산 화합물〔성분(2)〕의 치환기 R³및 R⁴는 수소 또는 탄소 원자수 1-10의 탄화수소기이고, 탄화수소기로서는 예를 들면 메틸, 에틸, 프로필, 부틸, 헥실, 옥틸, 싸이크로헥실, 페닐 등의 기가 권장된다. 이들의 화합물은 1종류 또는 2종류 이상의 구성단위로부터 이루는 2량체 이상의 쇄상 또는 환상의 화합물 형태로 사용할 수도 있다.General formula

Substituents R ³ and R ⁴ of the siloxane compound [component (2)] having a phosphorus structural unit are hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, and as the hydrocarbon group, for example, methyl, ethyl, propyl, butyl, hexyl Groups such as, octyl, cyclohexyl, phenyl and the like are recommended. These compounds can also be used in the form of the dimeric or more linear or cyclic compound which consists of one type or two or more types of structural units.

In the specific compound, for example, symmetric dihydrotetramethyldisiloxane, hexamethyldisiloxane, pentamethyltrihydrotrisiloxane, cyclic methylhydrotetrasiloxane (terminal methyl block), polymethylhydrosiloxane, polydimethylsiloxane (Terminal methyl blockade), polyphenylhydrosiloxane, polymethylphenylsiloxane, and the like are used.

The reaction between the organomagnesium complex [component (1)] and the siloxane can be, for example, Si-O / Mg + Al (or Zn) at a temperature between 0 and 150 ° C. in an inert reaction medium such as hexane, heptane, benzene or toluene. At a reaction rate of 0.3-5.

의 착결합의 생성이 적외 분광분석, 핵자기 공명 분광분석 및 분해물의 가스 분석으로부터 확인된다. 일반적으로 엄격한 조건, 예를 들면, 고온에서는 Si-0-M 결합이 생성하기 용이하고 방치조건에서는

의 결합이 주이다. 어떤 결합이 주가 되더라도 촉매의 성능에는 큰 차이가 없다. 좋기로는 Si-O/Mg＋Al(Zn)의 비는 0.3-5이다. 0.0 이하에서는 분자량 분포를 좁게 하는 효과가 나쁘고, 또 5 이하에서는 활성이 저하하기 때문에 좋지 않다. 다음에 적어도 1개의 할로겐 원자를 함유하는 티탄 또는 바나듐 화합물(3)로서는, 4염화티탄, 4취화티탄, 4옥화티탄, 에톡시 티탄트리크로라이드, 프로폭시티탄트리크로라이드, 부톡시티탄트리크로라이드, 디부톡시티탄디크로라이드, 트리부톡시티탄모노크로라이드, 4염화 바나듐, 3염화 바나딜, 모노부톡시바나딜디크로라이드, 디부톡시바나딜 모노크로라이드 등 티탄 및 바나듐의 할로겐화물 옥시할로겐화물, 알콕시할로겐화물의 단독 또는 혼합물이 사용된다.There are many uncertainties regarding the reaction pathway and reaction products, but the formation of Si-OM (M is Mg, Al or Zn) bonds and

The formation of complex bonds of is confirmed by infrared spectroscopy, nuclear magnetic resonance spectroscopy and gas analysis of digests. In general, under severe conditions, for example, at high temperatures, Si-0-M bonds are easy to form and under

The combination of is the main. No matter what the bond is, there is no big difference in the performance of the catalyst. Specifically, the ratio of Si-O / Mg + Al (Zn) is 0.3-5. In 0.0 or less, since the effect of narrowing molecular weight distribution is bad, and in 5 or less, activity falls, it is not good. Next, as a titanium or vanadium compound (3) which contains at least 1 halogen atom, it is a titanium tetrachloride, a titanium tetrachloride, a titanium tetrachloride, an ethoxy titanium trichloride, propoxy citatri trichloride, butoxy titanium trichrome. Halide oxy of titanium and vanadium, such as lide, dibutoxytitanium dichloride, tributoxytitanium monochloride, vanadium tetrachloride, vanadium trichloride, monobutoxy vanadil dichloride, and dibutoxy vanadil monochloride Halides, alkoxyhalides alone or in mixtures are used.

The reaction of the organomagnesium complex-siloxane reactant with the titanium or vanadium compound is carried out in an inert reaction medium, for example aliphatic hydrocarbons such as hexane, heptane, aromatic hydrocarbons such as benzene toluene, xylene, cyclohexane methylcyclohexane It performs at the temperature to 150 degreeC in alicyclic hydrocarbon.

The reaction ratio of the two catalyst components is about 0.05-50 Mol, especially 0.2-10 Mol, based on the magnesium and aluminum (or zinc) atoms of the organomagnesium complex-siloxane reactant with respect to 1 Mol of titanium or vanadium compound. Recommended. The hydrocarbon insoluble reaction product obtained by the reaction may be used as it is if the reaction is completed, but in order to increase the reproducibility of polymerization, it is preferable to separate from the reaction solution.

In the organic aluminum compound of one component of the catalyst (component [B]) according to the present invention As the use of the compound represented by the general formula AIR _n X _3n ⁵ alone or in mixture. In the formula, the hydrocarbon group having 1 to 20 carbon atoms represented by R ⁵ includes an aliphatic hydrocarbon, an aromatic hydrocarbon, and an alicyclic hydrocarbon. The group represented by X represents hydrogen, a halogen atom, alkoxy, aryloxy, siloxy, and n represents a number of 1-3. In particular, in order to obtain high activity, the value of n is desired to be 1.7 or more.

Specific examples of these compounds include triethyl aluminum, tri-n-propyl aluminum, triisopropyl aluminum, tri-n-butyl aluminum, triisobutyl aluminum, trihexyl aluminum, trioctyl aluminum, tridecyl aluminum , Tridodecyl aluminum, trihexadecyl aluminum, diethyl aluminum hydride, diisobutyl aluminum hydride, diethyl aluminum ethoxide, diisobutyl aluminum ethoxide, dioctyl aluminum butoxide, diisobutyl aluminum Chloride, dimethyl hydroxy aluminum dimethyl, ethyl methyl hydroxy aluminum diethyl, ethyl dimethyl siloxy aluminum diethyl, ethyl aluminum dichloride, butyl aluminum dichloride, ethyl aluminum diethoxide, ethyl methyl hydroxy aluminum ethyl Ride, trimethyl siloxyaluminum methyl chloride and the like and mixtures thereof are recommended.

Surprising catalysts are obtained by combining these alkylaluminum compounds with the above hydrocarbon insoluble solids, but especially trialkylaluminum and dialkylaluminum hydrides are good because the best activity is achieved. When negative phosphorus group X is introduced into trialkylaluminum or dialkylaluminum hydride, the activity tends to decrease, but each exhibits characteristic polymerization behavior, and it is possible to prepare useful polymers under high activity. For example, introduction of an alkoxy group reduces generation of scale in the polymerization reactor and facilitates molecular weight control.

The reaction of the [A] and [B] components of the catalyst of the present invention may be carried out with the addition of a positive catalyst component into the polymerization system and carried out with the progress of polymerization under the polymerization conditions, 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 1-3,000 mM with respect to 1 g of component [A].

As a polymerization method, conventional suspension polymerization and solution polymerization are possible, and the catalyst is a polymerization solvent, for example, aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as benzene, toluene and xylene, cyclohexane, methylcyclohexane, etc. The alicyclic hydrocarbon may be introduced into the reactor, and the ethylene may be indented at 1-50 kg / cm 2 under an inert atmosphere and the polymerization may proceed at a temperature of from room temperature to 150 ° C. Moreover, in order to adjust the molecular weight of a polymer, it is also possible to add hydrogen, a halogenated hydrocarbon, or an organometallic compound which is easy to cause chain transfer.

The catalyst of the present invention can also be used to polymerize in the presence of monoolefins such as propylene, butene-1 and hexene-1 and to efficiently polymerize propylene.

Examples of the present invention are shown below, and the present invention is not limited according to the embodiments thereof. In the examples, MI and R have the same meanings as described above, and the catalyst efficiency is 1 g of a solid component for 1 hour. The amount of polymer produced per 1 kg / cm 2 of ethylene pressure is expressed.

Example 1

(1) Reaction of organoaluminum-magnesium complex with siloxane

5.53 g of di-n-butyl magnesium and 0.76 g of triethylaluminum were added together with 40 ml of n-hexane to a 200 ml flask, and the composition was reacted under stirring at 80 ° C. for 2 hours, whereby AlMg ₆ (C ₂ H ₅ ) An organoaluminium-magnesium complex corresponding to ₃ (nC ₄ H ₉ ) ₁₂ is synthesized. Subsequently, this solution is cooled to 0 degreeC, and 40 ml of n-hexane solutions containing 5.5 g of symmetric tetramethyldihydrodisiloxane are added for 30 minutes, and a uniform solvent is obtained.

(2) Synthesis of Hydrocarbon Insoluble Solids

80 ml of the n-hexane solution containing the total amount of the hexane solution of the organoaluminium-magnesium complex and the siloxane solution and 40mMol of titanium tetrachloride were placed in a flask having a capacity of 300 ml from which water and oxygen were removed by dry nitrogen substitution, and then 5 ° C. The reaction is carried out for 4 hours under stirring. The resulting hydrocarbon insoluble solid is isolated and washed with n-hexane to give 124 g of solid. Ti content in solid is 13.2 weight%, and chlorine content is 37.5 weight% (the composition is represented by weight% hereafter).

(3) polymerization

(2) 5 mg of the hydrocarbon-insoluble reaction product synthesized in the step and 800 ml of triisobutyl aluminum were degassed together with 800 ml of hexane dehydrated and placed in a nitrogen-replaced 1.5 liter autoclave. The internal temperature of the autoclave is maintained at 85 ° C., hydrogen is 1.3 kg / cm 2, ethylene is pressurized at a pressure of 2.7 kg / cm 2, and the voltage combined with the vapor pressure of hexane is 4.7 kg / cm 2.

As the ethylene was replenished, the voltage was maintained at a gauge pressure of 4.7 kg / cm 2 and polymerization was carried out for 1 hour.

Obtained 327g of polymer, the catalyst efficiency was 24,200, MI was 6.1, and R was 30.

Example 2

An organic zinc-magnesium complex corresponding to composition ZnMg ₆ (C ₂ H ₅ ) ₂ (nC ₄ H ₉ ) ₁₂ synthesized in the same manner as in Example (1) with 5.53 g of di-n-butyl magnesium and 0.82 g of diethyl zinc. And 3.3 g of hexamethyldisiloxane were reacted to obtain a uniform solution. This solution and titanium tetrachloride 40mMol were made to react at -5 degreeC for 4 hours like Example (1), and 12.8g of solids were obtained.

Ti content in this solid was 14.2 weight%, and chlorine content was 42.6 weight%.

Polymerization was carried out in the same manner as in Example (1) using 5 ml of the hydrocarbon-insoluble solid and trihexyl aluminum 2 mMol, to obtain 317 g of a polymer.

Catalyst efficiency was 23,500, MI was 4.6, and R was 32.

Example 3-6

When the starting components, reaction conditions and catalyst components shown in Table 1 were used, catalyst synthesis and polymerization reactions were carried out in the same manner as in Example 1 except that the polymerization conditions of hydrogen partial pressure 1.0 kg / cm 2 and ethylene partial pressure 3.0 kg / cm 2 were used. The results shown are obtained.

[Table 1]

Example 7-8

(1) Reaction of Reaction of Organomagnesium Complex with Siloxane

In the same manner as in Example (1), 200 ml of a hexane solution containing 31.5 g of an organoaluminum-magnesium complex having a composition AlMg ₆ (C ₂ H ₅ ) ₂ (nC ₄ H ₉ ) ₁₂ was synthesized. Subsequently, this solution was kept at 30 degreeC, 200 ml of hexane solutions containing 12 g of cyclic methyl hydrotetrasiloxane were added, and it reacted at 80 degreeC for 5 hours, and the uniform solution was obtained.

(2) Synthesis of Hydrocarbon Insoluble Solids

Using the organomagnesium-siloxane reactant, a hydrocarbon-insoluble solid was obtained in the same manner as in Example (1) under the synthesis conditions shown in the second table.

(3) polymerization

Polymerization was carried out in the same manner as in Example (1), except that 5 mg of the hydrocarbon-insoluble solid synthesized in (2) and the organoaluminum component shown in Table 2 were used, and the results shown in the table were obtained.

[Table 2]

Claims (1)

[A] (1) General Formula MαMgβR ¹ mαR ₂ ² β [wherein M is an Al or Zn atom, represents an atom group of m and M, and R ¹ and R ² may be the same or different and are each hydrogen Or a hydrocarbon-soluble complex containing an organomagnesium represented by a hydrocarbon group having 1 to 16 carbon atoms, α and β are numbers greater than 0, and β / α are 0.5-10; (2) general formula

A reactant with a chain or cyclic siloxane compound having a structural unit in which R ³ and R ⁴ represents hydrogen or a hydrocarbon group having 1-10 carbon atoms, (3) a hydrocarbon insoluble reaction product produced by reacting with a titanium or vanadium compound containing at least one halogen atom, [B] General formula AIR ⁵ _n X _3-n [ _wherein R ⁵ is a hydrocarbon group of 1-20 carbon atoms, X is a group selected from hydrogen, halogen, alkoxy, aryloxy or siloxy group, n is 1- Ethylene or other olefins using a catalyst obtained by reacting the organoaluminum compound represented by the above formula.