KR840002105B1 - Process for preparing polymerisation catalyst - Google Patents

Abstract

A catalyst for polyolefin manufacture was the result of the reaction of an organo-magnesium compd. (1) and aluminum compd. (2). The reaction product was consecutively reacted with an hydroxy compd. (3) , and the final product was obtained by contacting it with a titanium or vanadium compd. (1) has the formula RMgX, where R = C1 - C20 alkyl or aryl gp., and X = halogen atom. (2) has the formula AlR'nX3-n, where R1 = C1 - C20 alkyl or aryl gp., X = halogen atom, and 0 n 3. (3) has the formula R"OH, where R" = C1 - C20 organic residual gp. The product, as a transition metal compd., is used for polymerization or copolymerization of olefin.

Description

Method for preparing a polyolefin production catalyst

The present invention relates to a process for producing polyolefins with new catalysts. More specifically, the present invention relates to an organic magnesium compound represented by the general formula RMgX (where R represents an alkyl or aryl group having 1 to 20 carbon atoms, and X represents a halogen atom) and a general formula

n

3이다)로 나타내는 알미늄 화합물을 반응시킨후, 일반식 R"OH(여기서 R"는 탄소수 1-20의 유기잔기를 표시)로 나타내는 하이드록시 화합물과 반응시켜서 얻어지는 화합물을 담체로 하고, 이에 티탄 화합물 및/또는 바나듐 화합물을 접촉처리함에 의하여 얻어지는 천이금속 화합물 성분과 유기금속화합물을 촉매로 하여 올레핀을 중합 또는 공중합하는 것을 특징으로 하는 폴리올레핀의 제조방법에 관한 것이다.ALR'nX ₃ -n where R 'is an alkyl or aryl group having 1-20 carbon atoms, X is a halogen atom and 0

n

After reacting the aluminum compound represented by (3), the compound obtained by reacting with a hydroxy compound represented by the general formula R " OH (where R " represents an organic residue having 1 to 20 carbon atoms) is used as a carrier. And / or olefin is polymerized or copolymerized using a transition metal compound component and an organometallic compound obtained by contact treatment of a vanadium compound as a catalyst.

Conventionally, since it has been found that a catalyst system composed of an organometallic compound and a transition metal compound can be used as an excellent catalyst for olefin polymerization in the technical field of this kind (Koko 32-1545, Kko 32-1546, Kko 32-2045 and others), numerous improved catalysts for olefin polymerization have been proposed. However, the catalytic activity in the production process of polyolefins is preferably as high as possible, and in particular, the development of a catalyst that is highly active enough to omit the catalyst removal step has been strongly demanded in recent years.

In view of this, the above-described improved catalyst is still low activity, and improvement is required. In addition, most of the catalyst systems described above have a low volume specific gravity of the produced polymer, have a low yield per unit volume of other polymerizers, which are difficult in handling of the polymer slurry, and difficult to handle the polymer powder. There was a flaw.

n

3이다)로 표시되는 알미늄 화합물을 반응시킨후 일반식 R"OH(여기서 R"는 탄소수 l-20의 유기잔기를 표시한다)로 표시되는 하이드록시 화합물과 반응시켜서 얻어지는 화합물을 담체로 하여, 이에 티탄 화합물 및/또는 바나듐 화합물을 접촉 담지시킨 천이금속 화합물 성분과 유기금속 화합물등을 촉매로 하여 올레핀을 중합 또는 공중합시키는 것을 특징으로 하는 폴리올레핀 제조방법에 관한 것으로 이 촉매를 사용함에 따라 극히 높은 고활성으로 올레핀을 중합 또는 공중합할 수가 있으며, 또 이때 생성하는 폴리마의 체적비중은 극히 높고, 전술한 기술적 과제를 해결하는 본 발명을 왼성한 것이다.The present invention relates to a catalyst for producing a new polyolefin and a polymerization or copolymerization method of an olefin using the catalyst which can solve such a technical problem at one time. That is, the present invention is an organic magnesium compound represented by the general formula RMgX (where R represents an alkyl or aryl group having 1 to 20 carbon atoms, X represents a halogen atom) and general formula ALR'nX ₃ -n (where R 'represents carbon number). An alkyl or aryl group of 1-20, X represents a halogen atom, and 0

n

A compound obtained by reacting an aluminum compound represented by Formula 3) with a hydroxy compound represented by the general formula R " OH (where R " represents an organic residue having 1 to 20 carbon atoms). The present invention relates to a polyolefin production method characterized by polymerizing or copolymerizing olefins using a transition metal compound component and an organometallic compound, etc., in which a titanium compound and / or vanadium compound are supported by contact. In addition, the olefin can be polymerized or copolymerized, and the volume ratio of the polymer produced at this time is extremely high, and the present invention solves the above technical problem.

Another advantage of the present invention is that it is possible to easily synthesize high melt index polymas and obtain the same melt index polymas at lower hydrogen concentrations, which would be extremely advantageous in terms of economy and productivity.

The structure of the carrier obtained in the reaction between the above-described RMgX, ALR'nX ₃ -n and R "OH used in the present invention is not detailed, but it is assumed that a new carrier is produced by the three-way reaction.

The reaction ratio of RMgX and ALR'nX ₃ -n used in the present invention can be selected widely, and the Mg / AL atomic ratio is 10 / 1-1 / 50, preferably 5 / 1-1 / l0 and 3 /. The range of 1-1 / 2 is preferable. Moreover, the reaction ratio at the time of reacting R "OH with these reactants can also be selected widely, and the (R + R ') / OH molar ratio is 10 / 1-1 / 20, Preferably 2 / 1-1 / 10 or 1 / The range of 1-1 / 5 is good, and all of these reactions are carried out under a solvent-free or inert diluent, and the reaction temperature is -100 ° C-200 ° C, preferably -20 ° C-100 ° C, preferably 0 ° C. The range of -100 DEG C is good, but there is no particular limitation on the reaction time, but the range of 1 minute-20 hours or 10 minutes-10 hours is preferable.

As the organic magnesium compound represented by the general formula RMgX (where R represents an alkyl group having 1 to 20 carbon atoms, an aryl group, X, or a halogen atom), a compound commonly known as a Grignard compound is used. Examples include methylmagnesium chloride, methylmagnesium bromide, methylmagnesium iodide, ethylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium iodide, n-propylmagnesium chloride, n-propylmagnesium bromide, n-propylmagnesium iodide , n-butylmagnesium chloride, n-butylmagnesium bromide, n-butylmagnesium iodide, isobutylmagnesium chloride, isobutylmagnesium bromide, isobutylmagnesium iodide, hexyl magnesium chloride, hexyl magnesium bromide, hexyl magnesium bromide Odide, octyl magnesium Low-grade, it may be mentioned octyl magnesium bromide, phenyl magnesium chloride, phenyl magnesium bromide, and compounds such as those of the ether-polymer complex.

As these ether compounds, various ether compounds, such as dimethyl ethyl, diethyl ether, diisopropyl ether, dibutyl ether, methyl ethyl ether, a diaryl ether, tetrahydrofuran, dioxane, anisole, are mentioned, for example. have. As the aluminum compound represented by the general formula ALR'nX ₃ -n (where R 'represents an alkyl or aryl group having 1 to 20 carbon atoms, X represents a halogen atom and 0≤n≤3), trimethyl aluminum and triethyl Aluminum, triisobutyl aluminum, trihexyl aluminum, tridecyl aluminum, diethyl aluminum chloride, diisobutyl aluminum chloride, ethyl aluminum sesquichloride methyl aluminum dichloride, ethyl aluminum dichloride, isobutyl aluminum dichloride, aluminum chloride, Aluminum bromide, aluminum iodide and mixtures thereof, and the like, with halogen compounds being particularly preferred.

Next, as the hydroxy compound represented by the general formula R " OH (where R " represents an organic residue having 1 to 20 carbon atoms), R " is preferably a hydrocarbon residue such as an alkyl group, an allyl group, an aralkyl group, and Even in the case of organic residues containing oxygen, nitrogen, oxo, anti-salt and other hetero elements, the groups consisting of these hetero elements can be used when they do not cause friction with other catalyst components of the present invention. Methanol, ethanol, isopropanol, butanol, pentanol, hexanol, octanol, phenol, chlorophenol, benzyl alcohol, methyl cellosolve, ethanol amine, and the like, and mixtures thereof.

A known method may be used as a method of wetly supporting a titanium compound and / or a vanadium compound on a carrier synthesized with a mixture of RMgX, ALR'nX ₃ -n and R''OH in the same manner as described above. For example, a solvent is present. A method of reacting the titanium compound and / or vanadium compound under heating or preferably in the presence of heat, preferably a method of co-pulverizing the carrier and the transition metal compound, etc. In the present invention, the co-pulverization method is particularly preferably used, The addition of a small amount of the transition metal compound enables the catalytic synthesis, thus eliminating the process of cleaning and removing the free transition metal compound. , Load mill, impact mill, and the like, and the conditions such as grinding temperature and grinding time can be easily determined by those skilled in the art according to the grinding method.

Generally the grinding temperature is 0 ° C-200 ° C, preferably 20 ° C-100 ° C and the grinding time is 0.5-50 hours, preferably 1-30 hours. Of course these operations should be carried out in an inert gas atmosphere and the moisture should be as small as possible.

The amount of the supported titanium compound and / or vanadium compound is preferably adjusted so that the amount of titanium or vanadium in the product is in the range of 0.5-20% by weight, and in order to obtain good balance of titanium or vanadium sugar and solid sugar activity. A range of 8% by weight is particularly good.

The titanium compound or vanadium compound used in the present invention is generally used as a Ziegler catalyst component without any particular limitation, but specifically titanium tetrachloride, titanium tetrabromide, monoethoxy titanium trichloride, diethoxy dichloride, tetra Tetravalent titanium compounds such as ethoxy titanium, dibutoxy titanium chloride, tetrabutoxy titanium, phenoxy titanium trichloride, trivalent titanium compounds such as titanium trichloride, titanium trichloride, aluminum trichloride and vanadium trichloride And trivalent vanadium compounds such as trivalent vanadium compounds, tetravalent vanadium compounds such as vanadium tetrachloride, vanadium oxychloride, and pentavalent vanadium compounds such as orthoalkyl vanadate.

The polymerization reaction of olefins using the catalyst of the present invention is carried out in the same manner as the olefin polymerization reaction using a normal Ziegler type catalyst. That is, all reaction is performed in the substantially absence of oxygen, water, etc. The polymerization conditions of the olefins are 20 to 300 ° C., preferably 50 to 180 ° C., and pressure to normal pressure to 70 kg / cm ^2, preferably 2 to 60 kg / cm ² . The molecular weight is controlled to some extent by changing the polymerization conditions such as the polymerization temperature and the molar ratio of the catalyst, but is effectively carried out by adding hydrogen to the polymerization system. Of course, using the catalyst of the present invention, two or more multi-stage polymerization reactions having different polymerization conditions such as hydrogen concentration and polymerization temperature are also performed without any problem.

The process of the present invention is applicable to the polymerization of all olefins polymerized as Ziegler catalysts, for example homopolymerization of α-olefins such as ethylene, propylene, 1-butene and ethylene and propylene, ethylene and 1-butene, propylene It is suitably used for copolymerization of 1-butene or copolymerization of olefins and diene compounds such as ethylene and 1,4-hexadiene, ethylene and ethylidene norbornene.

As the organometallic compound used in the present invention, an organometallic compound of Group I-IV of the periodic table known as one component of the Ziegler catalyst can be used, but organic aluminum and an organozinc compound are particularly preferable. Specific examples include organoaluminum compounds of the general formula R ₃ AL, R ₂ ALX, RALX ₂ , R ₂ ALOR, RAL (OR) ₂ , RAL (OR) X and R ₃ AL ₂ X ₃ (where R represents an alkyl group or an aryl group). X may be the same as or different from each other, X represents a halogen atom, or an organic zinc compound represented by the general formula R ₂ Zn (wherein R represents an alkyl group and may be the same or different). Ethyl aluminum, triisobutyl aluminum, trihexyl aluminum, trioctyl aluminum, tridecyl aluminum, diethyl aluminum chloride, ethyl aluminum sesquichloride, diethyl zinc, and mixtures thereof. In the present invention, the use amount of these organometallic compounds is not particularly limited, but can be used 0.1-1000 mo1 times as for the conventional transition metal compound.

The following examples are described, but these are for illustrative purposes only and the present invention is not limited thereto.

Example 1

(a) Preparation of Catalyst

The stirrer portion 500 ml flask was replaced with nitrogen, and 0.2 mol of tetrahydrofuran solution (2 mol / L) of ethyl magnesium chloride was added thereto, followed by addition of 0.2 mol of ethyl aluminum dichloride (n-hexane solution) under ice cooling with stirring. After reacting under reflux for 3 hours, 0.4 mol of ethanol was added thereto and reacted under reflux for 4 hours, followed by removing tetrahydrofuran and n-hexane of the solvent, and then drying at 150 ° C under reduced pressure.

1.86 g of titanium tetrachloride was added to 10 g of the carrier obtained as described above, and ball milling was carried out for 16 hours at room temperature under nitrogen atmosphere in 400 ml stainless steel pot containing 25 1/2 inch diameter stainless steel balls. . 1 g of the solid powder obtained after ball milling contained 40 mg of titanium.

(b) polymerization

2 L of stainless steel induction stirring unit autoclave was substituted with nitrogen, 1000 ml of hexane was added, 1 mmol of triethylaluminum and 20 mg of the solid described above were added thereto, and the temperature was raised to 90 ° C while stirring. The vapor pressure of hexane makes the system ² kg / cm ² , but hydrogen

Charge until 5.2 kg / cm ² · G, and then ethylene until the voltage reaches 10 kg / cm ² · G

The charge was initiated to initiate polymerization. Ethylene was continuously introduced so that the voltage was 10 kg / cm ² · G, and polymerization was performed for 1 hour. After completion of the polymerization, the polymer slurry was transferred to a beaker, and hexane was removed under reduced pressure to obtain belt index 9.3 and 173 g of white polyethylene having a volume ratio of 0.35. Catalytic activity was 45,000 g polyethylene / gTi · hr · C ₂ H ₄ pressure, 1,800 g polyethylene / g solid. hr · C ₂ H ₄ and pressure, and specific gravity was obtained by high-polyethylene is extremely high activity.

Example 2

A carrier and a catalyst were synthesized in the same manner as in Example 1, except that butylmagnesium chloride was used instead of ethylmagnesium chloride in Example 1 and 1.0 mol of ethanol was used instead of 0.4 mol of ethanol. When the polymerization was carried out for 1 hour, 245 g of white polyethylene having a melt index of 11.5 and a volume ratio of 0.39 was obtained.

The catalytic activity was 2,550 g polyethylene / g solids, hr · C ₂ H ₄ pressure, 63,800 g polyethylene / gTi · hr · C ₂ H ₄ pressure, and extremely high activity.

Example 3

In Example 1, 0.15 mol of diethyl ether solution of butyl magnesium chloride was used instead of 0.2 mol of tetrahydrofuran solution of ethyl magnesium chloride, and 0.05 mol of aluminum trichloride instead of ethyl aluminum dichloride, and the reaction was carried out under reflux with diethyl ether. The organic magnesium compound and the aluminum compound were reacted in the same manner as in Example 1 except that the reaction was carried out for 4 hours. Subsequently, 0.25 mol of ethanol was added to carry out the same reaction to obtain a solid carrier. Then, titanium tetrachloride was supported in the same manner to obtain a solid containing 39 mg of titanium in 1 g of the solid.

Polymerization was carried out in the same manner as in Example 1 using the solid catalyst described above to obtain 306 g of white polyethylene having a melt index of 12.4 and a volume ratio of 0.38. The activity was very high at 3,190 g polyethylene / g solid. · Hr · C ₂ H ₄ pressure and 81,800 g polyethylene / gTi · hr · C ₂ H ₄ pressure, and the volume specific gravity was extremely high.

Example 4

In Example 1, 0.2 mol of diethyl ether solution of ethyl magnesium bromide was used instead of tetrahydrofuran solution of ethyl magnesium chloride, and 0.2 mol of diethyl aluminum chloride instead of ethyl aluminum dichloride was used for 4 hours under reflux of diethyl ether. It was done. Subsequently, a carrier and a catalyst were synthesized in the same manner as in Example 1 except that 0.8 mol of methanol was added, and the catalyst was polymerized in the same manner as in Example 1, and the melt index 12.1 and 212 g of white polyethylene having a volume ratio of 0.38 were Obtained. The catalytic activity was 2,210 g polyethylene / g solids, hr · C ₂ H ₄ pressure, 55,200 g polyethylene / gTi · hr · C ₂ H ₄ pressure, extremely high activity and high volume specific gravity.

Example 5

Using 20 mg of the catalyst synthesized in Example 1, 1 mmol of triethylaluminum and 1000 ml of hexane, hydrogen was injected to 5.2 kg / cm ² · G at 90 ° C., followed by an ethylene-propylene mixed gas containing 2 mol% of propylene. The polymerization was carried out for 1 hour so as to maintain the pressure of the autoclave at 10 kg / cm ² to obtain 174 g of a white polymer having a melt index of 9.1, a volume ratio of 0.36, and 4.8 methyl groups per 1,000 carbon atoms. Catalytic activity is 1,810 g polyethylene / g solid. hr pressure, 45,300 g polyethylene / gTi * hr * pressure, it was extremely high activity, and volume specific gravity was also high.

Claims (1)

When composed of a transition metal compound and an organometallic compound, a catalyst used to polymerize or copolymerize olefins is prepared in the production method, which comprises: (1) a general formula of RMgX, wherein R is an alkyl or aryl group having 1-20 carbon atoms and X is a halogen atom. And an organic magnesium compound represented by the formula ALR'nX ₃ -n, wherein R 'represents an alkyl or aryl group having 1 to 20 carbon atoms, X represents a halogen atom, and 0

n

A compound obtained by reacting an aluminum compound represented by Formula 3) with a hydroxy compound represented by the general formula R " OH (where R " represents an organic residue having 1 to 20 carbon atoms); A method for producing a catalyst for producing polyolefin, characterized in that the transition metal compound component is obtained by contact treatment with a titanium compound, a vanadium compound or one of these compounds.