JPH0457651B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] This invention is applicable to, for example, raw materials for polymers, base materials used for preparing lubricating oils, base materials used for preparing cosmetics, raw materials for manufacturing various chemical products, etc. The present invention relates to a method for producing a propylene-based low polymer used for. More specifically, the propylene type mainly has a degree of polymerization of 2 to 10 and can produce propylene low polymers having a vinyl group at the molecular end or low polymers of propylene and olefins other than propylene with high selectivity. The present invention relates to a method for producing a low polymer. [Prior art and its problems] It is generally known that a Ziegler-Natsuta catalyst is used in addition to a solid catalyst containing an alkali metal in the production of propylene-based low polymers. - A method of polymerizing propylene using a potassium catalyst, a catalyst consisting of a combination of a nickel compound and an aluminum compound, or a catalyst consisting of a titanium compound and an organoaluminum compound is known. However, the products obtained by these production methods are polymers having a vinyl group at the molecular end, 2-methylpentene-2, 4-methylpentene-2, 2,3-dimethylbutene-2, hexene-2, etc. It is a mixture of various components such as various internal olefins including dimers of 2-methylpentene-1 and 2,3-dimethylbutene-1 and vinylidene compounds including dimers of 2-methylpentene-1 and 2,3-dimethylbutene-1. Therefore, in order to obtain industrially useful propylene-based low polymers with vinyl groups at the molecular ends, complex separation operations are required. There was a problem that the selectivity of merging itself was low. In particular, no conventional methods have been found for the low polymerization of propylene and olefins other than propylene. -Methyloctene-1 is not known to be obtained. [Means for solving the above problems] This invention has been made based on the above circumstances. That is, the object of the present invention is to produce a propylene low polymer or a low polymer of propylene and an olefin other than propylene with a high selectivity, mainly having a degree of polymerization of 2 to 10 and having a vinyl group at the end of the molecule. An object of the present invention is to provide a method for producing a propylene-based low polymer. In order to achieve this objective, the inventors have made extensive studies and found that the use of a catalyst consisting of a specific transition metal compound component and a specific organometallic compound component has been found to be industrially useful. The present invention was achieved by discovering that a propylene low polymer having a vinyl group at the molecular end or a low polymer of propylene and an olefin other than propylene can be efficiently produced with high selectivity. That is, the structure of the first invention is to produce a propylene-based low polymer by reacting propylene alone or propylene with an olefin other than propylene using a catalyst consisting of a transition metal compound component and an organometallic compound component. The manufacturing method is characterized in that an alkyl-substituted cyclopentadienyl compound of zirconium and/or hafnium is used as the transition metal compound component, and a condensation product of an organoaluminum compound and water is used as the organometallic compound component. The second aspect of the invention is a method for producing a propylene-based low polymer, in which propylene alone or propylene and an olefin other than propylene are combined using a catalyst comprising a transition metal compound component and an organometallic compound component. In a method for producing a propylene-based low polymer by reaction, an alkyl-substituted cyclopentadienyl compound of zirconium and/or hafnium and an electron-donating compound are used as the transition metal compound component, and as the organometallic compound component A method for producing a propylene-based low polymer, characterized in that a condensation product of an organoaluminum compound and water is used, and the third aspect of the invention is characterized in that a catalyst comprising a transition metal compound component and an organometallic compound component is used. In the method for producing a propylene-based low polymer by reacting propylene alone or propylene with an olefin other than propylene, an alkyl-substituted cyclopentadienyl compound of zirconium and/or hafnium as the transition metal compound component. and a condensation product of an organoaluminum compound and water as the organometallic compound component to perform low polymerization of propylene or low polymerization of propylene and an olefin other than propylene in the presence of hydrogen. This is a method for producing a propylene-based low polymer. The structure of the fourth invention is to produce a propylene-based low polymer by reacting propylene alone or propylene with an olefin other than propylene using a catalyst consisting of a transition metal compound component and an organometallic compound component. In the method, an alkyl-substituted cyclopentadienyl compound of zirconium and/or hafnium and an electron-donating compound are used as the transition metal compound component, and a condensation product of an organoaluminum compound and water is used as the organometallic compound component. This is a method for producing a propylene-based low polymer, which is characterized in that low polymerization of propylene or low polymerization of propylene and an olefin other than propylene is performed in the presence of hydrogen. The alkyl-substituted cyclopentadienyl compound of zirconium or hafnium (hereinafter sometimes referred to as a cyclopentadienyl compound) can be represented by the following formula [1]. (R ₅ C ₅ ) _n・M・X _4-n [1] (However, in formula [1], R represents an alkyl group having 1 to 20 carbon atoms, and R ₅ C ₅ is substituted with an alkyl group. Cyclopentadienyl group [1] Hereinafter abbreviated as alkyl-substituted cyclopentadienyl group.]
, M represents a zirconium atom or a hafnium atom, and X represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a halogen. Moreover, m shows a real number of 2-4. ) The alkyl group represented by R or X in the above formula [1] has 1 to 20 carbon atoms, and specific examples include:
Methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, amyl group, hexyl group, heptyl group, octyl group, nonyl group, capryl group, undecyl group, lauryl group, tridecyl group, myristyl group, pentadecyl group , cetyl group,
heptadecyl group, stearyl group, nonadecyl group,
Examples include eicosyl group. The halogen represented by X in the formula [1] is not particularly limited, but chlorine is preferred. More specifically, the alkyl-substituted cyclopentadienyl compound represented by the formula [1] is, for example, [(CH ₃ ) ₅ C ₅ ] ₂ HfCl ₂ , [(CH ₃ ) ₅ C ₅ ] ₂ ZrCl ₂ , [(C ₂ H ₅ ) ₅ C ₅ ] ₂ HfCl ₂ , [(C ₂ H ₅ ) ₅ C ₅ ] ₂ ZrCl ₂ , [(C ₃ H ₇ ) ₅ C ₅ ] ₂ HfCl ₂ , [(C ₃ H ₇ ) ₅ C ₅ ] ₂ ZrCl ₂ , [(CH ₃ ) ₅ C ₅ ] ₂ HfHCl, [(CH ₃ ) ₅ C ₅ ] ₂ ZrHCl, [(C ₂ H ₅ ) ₅ C ₅ ] ₂ HfHCl, [ (C ₂ H ₅ ) ₅ C ₅ ] ₂ ZrHCl, [(C ₃ H ₇ ) ₅ C ₅ ] ₂ HfHCl, [(C ₃ H ₇ ) ₅ C ₅ ] ₂ ZrHCl, [(CH ₃ ) ₅ C ₅ ] ₂ Hf(CH ₃ ) ₂ , [(CH ₃ ) ₅ C ₅ ] ₂ Zr
( _CH3 ) _{2 ,} [( _{C2H5 )} ( _CH3 ) _4C5 ] _{2HfCl2 , [} ( _{C2H5 )} ( _CH3 ) _4C5 ] _{2ZrCl2 ,} etc. . These can be used alone or in combination of two or more. Among the various alkyl-substituted cyclopentadienyl compounds, [(CH ₃ ) ₅ C ₅ ] ₂ HfCl ₂ , [(CH ₃ ) ₅ C ₅ ] ₂ ZrCl ₂ , [(CH ₃ ) ₅ C ₅ ] ₂ HfHCl , [(CH ₃ ) ₅ C ₅ ] ₂ ZrHCl, [(CH ₃ ) ₅ C ₅ ] ₂ Hf(CH ₃ ) ₂ , [(CH ₃ ) ₅ C ₅ ] ₂ Zr
(CH ₃ ) ₂ , [(C ₂ H ₅ )(CH ₃ ) ₄ C ₅ ] ₂ HfCl ₂ , [(C ₂ H ₅ )(CH ₃ ) ₄ C ₅ ] ₂ ZrCl ₂ , etc. Dienyl compounds are preferred, and hafnium compounds are particularly preferred. Examples of the electron-donating compound that can be used in the present invention include organic compounds containing oxygen, nitrogen, phosphorus, or sulfur, or olefins. Specifically, amines, amides, ketones, nitriles, phosphines, phosphoramides, esters, ethers, thioethers,
Examples include thioesters, acid anhydrides, acid amides, acid halides, aldehydes, and organic acids. More specifically, organic acids such as aromatic carboxylic acids such as benzoic acid and p-oxybenzoic acid; acid anhydrides such as succinic anhydride, benzoic anhydride, and p-toluic anhydride; acetone, methyl ethyl ketone, Methyl isobutyl ketone, acetophenone,
3 carbon atoms such as benzophenone and benzoquinone
-15 ketones; aldehydes having 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, naphthaldehyde; methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, Octyl acetate, cyclohexyl acetate, ethyl propionate, ethyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate,
Methyl methacrylate, ethyl crotonate, ethyl pivalate, dimethyl maleate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzoate Benzyl acid, methyl toluate, ethyl toluate, amyl toluate, ethyl ethylbenzoate, methyl anisate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, ethyl p-butoxybenzoate, ethyl o-chlorobenzoate , ethyl naphthoate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethylene carbonate, and other esters with a carbon number of 2 to 18; carbon numbers such as acetyl chloride, benzyl chloride, toluyl chloride, anisyl chloride, etc. Acid halides with a carbon number of 2 to 15; ethers with a carbon number of 2 to 20, such as methyl ether, ethyl ether, isopropyl ether, n-butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether, and ethylene glycol butyl ether; Acid amides such as acetic acid amide, benzoic acid amide, and toluic acid amide; amines such as tributylamine, N,N'-dimethylpiperazine, tribenzylamine, aniline, pyridine, picoline, and tetramethylethylenediamine; acetonitrile, benzonitrile, Nitriles such as tolnitrile; tetramethylurea, nitrobenzene, lithium butyrate,
Examples include piperidine and toluidine. In addition, phosphorus compounds have the general formula PO(OR ¹ ) ₃ or PR ¹ ₃ (wherein R ¹ is an aliphatic hydrocarbon group, an unsaturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, a halogen atom, or Examples include phosphoric acid or phosphite esters and phosphines represented by (representing a hydrogen atom). Specifically, trimethyl phosphate,
Phosphate esters or their halides such as triethyl phosphate, tributyl phosphate, triphenyl phosphate, diphenyl phosphate chloride, phenyl phosphate dichloride, methyl phosphite, ethyl phosphite, butyl phosphite, triphenyl phosphite, phosphorous Phosphite esters such as acid triphenyl, tri-2,4-di-tert-butylphenyl phosphite, diphenyl phosphite chloride, phenyl phosphite dichloride, or their halides, triethylphosphine, tributylphosphine, diphenyl dichloro Examples include phosphines such as phosphine. Among these, preferred are esters, ethers, ketones, amines, phosphoric acid compounds, and the like. Particularly preferred are alkyl esters of aromatic carboxylic acids, alkyl esters of aromatic carboxylic acids having 1 to 4 carbon atoms, such as benzoic acid, p-methoxybenzoic acid, p-ethoxybenzoic acid, and toluic acid; Also preferred are aromatic ketones, aromatic carboxylic acid anhydrides such as benzoic anhydride, ethers such as ethylene glycol ether, and nitrogen-containing compounds such as piperidine and triidine. The alkyl-substituted cyclopentadienyl compound and the electron-donating compound react by mixing them, and a reaction product thereof is obtained. The reaction product is presumed to be a coordination compound in which the electron-donating compound is coordinated to the alkyl-substituted cyclopentadienyl compound. The alkyl-substituted cyclopentadienyl compound [referred to as (a)]. ] and the electron-donating compound [(b). ] The ratio (b)/(a) is usually a molar ratio of 0.1 to
10, preferably 0.5-2. As the organoaluminum compounds, compounds represented by the general formulas AlR ² ₃ , AlR ³ ₂ Y, and Al ₂ R ⁴ ₃ Y ₃ are widely used. Here, R ² , R ³ and R ⁴ are cycloalkyl groups,
It is an aryl group or an alkyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, and Y represents a hydrogen atom, a halogen atom such as chlorine or bromine, or an alkoxy group such as a methoxy group or an ethoxy group. Examples of the organoaluminum compound represented by the above general formula include trimethylaluminum,
Triethyl aluminum, tripropyl aluminum, triisopropyl aluminum, tributyl aluminum, triisobutyl aluminum,
Trialkylaluminum such as triamylaluminum and trioctylaluminum; dialkylaluminum monohalide such as diethylaluminum monochloride, diisopropylaluminum monochloride, diisobutylaluminum monochloride, dioctylaluminum monochloride;
Examples include ethylaluminum sesquichloride, diethylaluminum hydride, dimethylaluminum ethoxide, and diethylaluminum methoxide. In this invention, as long as at least one type of trialkylaluminum is contained, one type of the various organoaluminum compounds described above can be used alone, or two or more types thereof can be used in combination. Among the various organic aluminum compounds as essential components, trialkylaluminum represented by the general formula AlR ⁵ ₃ (wherein R ⁵ represents an alkyl group having 1 to 5 carbon atoms) is preferred, particularly Trimethylaluminum, triethylaluminum, etc. are preferred. In the method of the first invention, propylene alone or propylene and propylene are mixed in the presence of a catalyst obtained from the alkyl-substituted cyclopentadienyl compound of zirconium or hafnium, the organoaluminum compound, and the condensation product of water. By polymerizing other olefins, propylene-based low polymers can be produced with high selectivity. It is generally known that aluminoxane is produced by the condensation reaction between organoaluminum compounds and water, but there are no particular restrictions on the water used for the reaction, and water containing some impurities may be used as long as it does not interfere with the production of the aluminoxane. It may be hot. Furthermore, as the water to be reacted, in addition to the direct reaction, for example, water of crystallization in a hydrated salt can also be used. Examples of the aluminoxane obtained by condensing the organic aluminum compound and the water include methylaluminoxane, ethylaluminoxane, propylaluminoxane, isopropylaluminoxane, butylaluminoxane, isobutylaluminoxane, amylaluminoxane, and the like. The condensation product of the organoaluminum compound and water is not limited in its molecular weight, nor is there any particular limitation in its preparation method. For example, the organic aluminum compound and water may be condensed in the low polymerization reaction zone, or the organic aluminum compound and water may be reacted and prepared before being supplied to the low polymerization reaction zone. Furthermore, the resulting condensation product may be supported on a solid carrier for use, or the condensation product may be coexisting with other organoaluminum compounds. The blending ratio when reacting the alkyl-substituted cyclopentadienyl compound or the reaction product of the alkyl-substituted pentadienyl compound and the electron-donating compound with the condensation product of the organoaluminum compound and water is usually such that aluminum atoms / in zirconium or hafnium atomic ratio
It is preferable to adjust it to 10 to 5000. As the propylene, for example, one obtained by cracking petroleum gas or fractional distillation of natural gas can be used. The olefin other than propylene is not particularly limited, but α-olefins having about 2 to 16 carbon atoms, preferably about 2 to 8 carbon atoms, especially olefins containing a vinyl terminal group, etc. can be suitably used. Examples of α-olefins that can be suitably used include ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene,
1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1,
4-pentadiene, 1,5-heptadiene, 1,
Examples include 7-octadiene, 1,9-decadiene, 4-methyl-1-pentene, neohexene, vinylcyclohexane, and 4-vinylcyclohexene. Among these, particularly preferred are ethylene,
1-butene, 1-pentene, 1-hexene, 1-
Heptene, 1-octene. The olefins other than propylene may be used alone or in combination of two or more. There is no particular restriction on the ratio of the propylene to the olefin other than propylene,
(Propylene): (Olefin other than propylene)
By appropriately selecting the value of , the composition of the propylene-based low polymer of the product can be adjusted. Here, in order to increase the selectivity of the terminal vinyl compound, it is desirable to increase the ratio of the propylene to the olefin other than the propylene. The olefins other than propylene may be supplied to the reaction system separately, or may be mixed in advance and supplied. Regarding the low polymer reaction of propylene alone or propylene and an olefin other than propylene, the reaction temperature is not particularly limited, but is usually 0 to 100°C, preferably 20 to 80°C, and any temperature The low polymerization reaction can be carried out at a low pressure, for example, 10 Kg/cm ² G or less, or, if desired, under normal pressure. Regarding the reaction temperature, to explain further, if the reaction temperature is low, products with a high degree of polymerization are likely to be produced, and conversely, if the reaction temperature is high, products with a low degree of polymerization such as dimers and trimers are obtained. Therefore, the reaction temperature may be appropriately determined depending on the desired product. However, 0~
If the temperature is outside the range of 100°C, the activity of the catalyst may decrease. A solvent can be used in the low polymerization reaction of propylene alone or the low polymerization reaction of propylene and an olefin other than propylene. Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, mesitylene, naphthalene, tetralin, butylbenzene, p-cymene, cyclohexylbenzene, diethylbenzene, pentylbenzene, dipentylbenzene, dodecylbenzene, and biphenyl. ;2-methylbutane, hexane, 2-
Methylpentane, 2,2-dimethylbutane, 2,
3-dimethylbutane, heptane, octane, 2,
Aliphatic hydrocarbons such as 2,3-trimethylpentane, isooctane, nonane, 2,2,5-trimethylhexane, decane, and dodecane; and other fats such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, and decalin. Cyclic hydrocarbons include petroleum ether, petroleum benzine, petroleum naphtha, ligroin, industrial gasoline, kerosene, and the like. Polymerization methods include solution polymerization method, bulk polymerization method,
Although any method such as gas phase polymerization may be used, solution polymerization is preferred from the viewpoint of catalytic activity. According to the method for producing a propylene-based low polymer of this invention, the following general formula is mainly used: (However, in the formula, q represents a real number from 1 to 9.) To obtain a low polymer compound of propylene having a vinyl group at the molecular terminal represented by the formula under simple and mild conditions as a high polymer. Can be done. According to further consideration by the inventor,
When the propylene alone or propylene and an olefin other than propylene are subjected to low polymerization, the presence of hydrogen under the above reaction conditions improves the polymerization activity, and surprisingly, the presence of hydrogen during the polymerization reaction improves the polymerization activity. It has been found that the conversion rate of olefin can be improved without causing a hydrogenation reaction of olefin and reducing the selectivity of olefin. That is, in the methods of the third and fourth inventions, in the presence of hydrogen and a catalyst obtained from the alkyl-substituted cyclopentadienyl compound of zirconium or hafnium, the organoaluminum compound, and the condensation product of water, A propylene-based low polymer can be produced with high selectivity by polymerizing propylene alone or propylene and an olefin other than propylene. As the hydrogen, hydrogen obtained by, for example, modification of water gas, gasification of petroleum, complete gasification of coal, modification of natural gas, etc. can be used. The amount of hydrogen used is arbitrary, but it is usually 1 to 100 mol%, and 5 to 100 mol% based on the raw material propylene.
It is preferably used within the range of 20 mol%. The type and proportion of the propylene-based low polymer obtained by the method of the present invention can be variously adjusted depending on the type of olefin other than propylene used, the proportion of this olefin and propylene used, reaction conditions, etc. The propylene low polymer or the low polymer of propylene and an olefin other than propylene that can be obtained by the method of the present invention can be suitably used as a variety of chemical synthesis raw materials, polymer raw materials, lubricating oil base materials, cosmetic base materials, etc. can do. [Example] Next, the present invention will be explained in more detail by showing examples and comparative examples of the present invention. Example 1 Preparation of aluminum catalyst component 200 ml of toluene was placed in a reaction vessel, and 47.4 ml (492 mmol) of trimethylaluminum and copper sulfate pentahydrate (Cu ₂ SO ₄ .5H ₂ O) were added.
35.5 g (142 mmol) was added and reacted at 20° C. for 24 hours under an argon stream. Copper sulfate was filtered off from the resulting reaction solution, and toluene was distilled off to obtain 12.4 g of methylaluminoxane. Here, the obtained methylaluminoxane had a molecular weight of 721 as measured by the benzene freezing point depression method. Low polymerization of propylene Toluene was added to an autoclave with an internal volume of 1.
400 ml, 6 mmol of the methylaluminoxane obtained above in terms of aluminum equivalent, and 0.01 mmol of bis(pentamethylcyclopentadienyl)zirconium dichloride were sequentially added,
The temperature was raised to 50°C. Next, propylene was continuously introduced into the autoclave to bring the partial pressure of propylene to 6Kg/ ^cm2.
The reaction was carried out at 50° C. for 4 hours while maintaining the temperature. After the reaction is complete, the product is deashed using 150 ml of 3N hydrochloric acid to form a mixture of propylene-based low polymers.
30.3g was obtained. Analysis of the resulting mixture of propylene-based low polymers revealed that the dimer was 4.7g, the trimer was 1.8g,
The amount of low polymer of tetramer or higher was 23.8 g, and the average degree of polymerization was 4.6. In addition, the obtained mixture of propylene-based low polymers was analyzed by infrared absorption spectroscopy and
As a result of ¹ HNMR (270MHz) spectrum analysis, it was found that it is a propylene-based low polymer with a vinyl group at the molecular end (absorption peaks: 1640 cm ^-1 , 994 cm ^-1 ,
The content of propylene-based low polymer having a vinylidene group at the molecular ^end (absorption peak: 884 cm ^-1 ) was 8%. Furthermore, as a result of analyzing the dimer, 4-
Methyl-pentene-1 was the main component, and the selectivity was 98%. The results are shown in Table 1. Examples 2 to 15 Examples 2 to 15 were carried out in the same manner as in Example 1, except that the catalyst components and polymerization temperature were changed as shown in Table 1. The results are shown in Table 1. Example 16 In Example 1, bis(pentamethylcyclopentadienyl) hafnium dichloride was used instead of bis(pentamethylcyclopentadienyl) zirconium dichloride, and hexane was used instead of toluene as the polymerization solvent. teeth,
It was carried out in the same manner as in Example 1 above. The results are shown in Table 1. Example 17 In Example 1 above, bis(pentamethylcyclopentadienyl)zirconium dichloride
Example 1 except that 0.01 mmol of the reaction product obtained by reacting equimolar amounts of bi(pentamethylcyclopentadienyl) hafnium dichloride and ethyl benzoate was used as the hafnium atom instead of 0.01 mmol. It was carried out in the same manner. The results are shown in Table 1. Example 18 Toluene 400 was added to an autoclave with an internal volume of 1.
ml and 6 mmol of trimethylaluminum were added, followed by 3.9 mmol of water and allowed to react for 10 minutes. Next, add 0.01 mmol of bis(pentamethylcyclopentadienyl) hafnium dichloride,
The temperature was raised to 50°C. Thereafter, propylene was continuously introduced into the autoclave, and while the propylene partial pressure was maintained at 8 kg/cm ² G, the reaction was carried out at 50° C. for 4 hours to obtain a propylene-based low polymer. The treatment after the reaction was carried out in the same manner as in Example 1 above. The results are shown in Table 1. Example 19 In Example 1, bis(pentamethylcyclopentadienyl) hafnium dichloride was used instead of bis(pentamethylcyclopentadienyl) zirconium dichloride, and methylaluminoxane was used as the organoaluminum compound used during polymerization. Example 1 was carried out in the same manner as in Example 1, except that a mixture of 6 mmol of methylaluminoxane (aluminum equivalent) and 6 mmol of trimethylaluminum was used. The results are shown in Table 1. Example 20 In Example 1, bis(n-butyltetramethylcyclopentadienyl)hafnium dichloride was used instead of bis(pentamethylcyclopentadienyl)zirconium dichloride, and the reaction temperature was changed from 80 to 55°C. , the reaction time was changed from 4 hours to 2 hours, and the hydrogen partial pressure was changed to 1 kg/
The same procedure as in Example 1 was carried out except that cm ² G was introduced. The results are shown in Table 1. Note that bis(n-butyltetramethylcyclopentadienyl)hafnium dichloride was prepared as follows. Preparation of transition metal compound 15 g (77.7 mmol) of 2,3,4,5-tetramethyl-2-cyclopenten-1-one and 116.6 mmol of n-butyllithium were mixed in 100 ml of ether solvent under an argon atmosphere at a temperature of -50°C. 3 under the conditions of
A reaction solution was obtained by reacting for a period of time. 100 ml of distilled water was added to the resulting reaction solution, and the ether layer was separated. On the other hand, the aqueous layer was extracted with ether, and the ether was removed together with the above fractionated ether using an evaporator. The obtained liquid was refluxed and dehydrated in 200 ml of benzene with 1 g of p-toluenesulfonic acid for 2 hours, and 9.7 g (57.5 mmol, yield:
74%). Next, 7 g (42 mmol) of this n-butyltetramethylcyclopentadiene and 69 mmol of n-butyllithium were added to 90 ml of p-xylene, mixed at -10°C, and returned to room temperature. Allowed time to react. Then, the supernatant liquid was replaced with hexane, 3.2 g (10 mmol) of hafnium tetrachloride was added, and then
The reaction was carried out under reflux for 2 hours. The resulting reaction slurry was filtered under a stream of argon, the solid components were washed with p-xylene, and the washings were concentrated together with the filtrate. Add 100ml of hexane to the concentrated reaction product,
Filtration was performed again and the filtrate was collected. After concentrating this filtrate, crystals were precipitated at a temperature of -50°C. Next, the precipitated solid component was separated and recrystallized in a hexane solvent at a temperature of -50°C. The obtained solid component was separated and dried to obtain 1.2 g of product (yield 24%). When this product was subjected to ¹ HNMR (270MHz) spectrum analysis and elemental analysis, it was confirmed that this product was bis(n-butyltetramethylcyclopentadienyl)hafnium dichloride. Example 21 The same procedure as in Example 20 was carried out, except that bis(ethyltetramethylcyclopentadienyl)hafnium dichloride was used instead of (n-butyltetramethylcyclopendienyl)hafnium dichloride. It was carried out. The results are shown in Table 1. Note that bis(ethyltetramethylcyclopentadienyl)hafnium dichloride was prepared in Example 19 above.
The transition metal compound was prepared in the same manner as in Example 20, except that ethyllithium was used in place of n-butyllithium. Example 22 Same as Example 20, except that (n-butyltetramethylcyclopentadienyl)zirconium dichloride was used instead of (n-butyltetramethylcyclopentadienyl)hafnium dichloride. It was carried out in the same manner. The results are shown in Table 1. In addition, (n-butyltetramethylcyclopentadienyl)zirconium dichloride is
The transition metal compound in Example 20 was prepared in the same manner as in Example 20, except that zirconium tetrachloride was used in place of hafnium tetrachloride. Comparative Example 1 A propylene-based low polymer was prepared in the same manner as in Example 1 except that bis(cyclopentadienyl)zirconium dichloride was used instead of bis(pentamethylcyclopendienyl)zirconium dichloride. I got it. The results are shown in Table 1. Comparative Example 2 A propylene-based low polymer was prepared in the same manner as in Comparative Example 1, except that bis(cyclopentadienyl)hafnium dichloride was used instead of bis(cyclopentadienyl)zirconium dichloride. Obtained. The results are shown in Table 1. Comparative Example 3 A propylene-based low polymer was obtained in the same manner as in Comparative Example 1, except that bis(cyclopentadienyl)titanium dichloride was used instead of bis(cyclopendienyl)zirconium dichloride. Ta. The results are shown in Table 1.

【table】

[Table] Example 23 Preparation of aluminum catalyst component An aluminum catalyst component was prepared in the same manner as in Example 1 above. Low polymerization of propylene and olefins other than propylene Toluene was added to an autoclave with an internal volume of 1.
400 ml, 6 mmol of the methylaluminoxane obtained above in terms of aluminum equivalent, and 0.01 mmol of bis(pentamethylcyclopentadienyl) hafnium dichloride were added in order, and 50
The temperature was raised to ℃. Then, in an autoclave, 1-butene 20
g and propylene were introduced, and while the propylene partial pressure was maintained at 2 kg/cm ² G, the reaction was carried out in a closed system at a temperature of 50° C. for 4 hours. After the reaction was completed, the product was deashed using 150 ml of 3N hydrochloric acid to obtain 16.7 g of oligomer. ¹ HNMR (270M
Hz) spectrum analysis revealed that the content of low polymers with vinyl groups at the molecular ends was 79%.
%, and the content of the polymer having a vinylidene group at the end of the molecule was 21%. The results are shown in Table 2. Example 24 In Example 23 above, the amount of 1-butene used was
Change from 20g to 40g, propylene partial pressure 2Kg/cm ²
Example 23 except that G was changed to 5 Kg/cm ² G and hydrogen was introduced at a hydrogen partial pressure of 1 Kg/cm ² G.
It was carried out in the same manner. The results are shown in Table 2. Example 25 In Example 23 above, the propylene partial pressure was
The procedure was carried out in the same manner as in Example 23, except that propylene was continuously introduced so that the pressure was changed from Kg/ ^{cm 2} G to 6.5 Kg/cm ² G and the total pressure was maintained at 9 Kg/cm 2 G. . The results are shown in Table 2. Example 26 Same as Example 23, except that 40 g of 1-pentene was used instead of 20 g of 1-butene, and the partial pressure of propylene was changed from 2 Kg/cm ² G to 3 Kg/cm ² G. It was carried out in the same manner. The results are shown in Table 2. Example 27 Same as Example 23, except that 34 g of 1-hexene was used instead of 20 g of 1-butene, and the partial pressure of propylene was changed from 2 Kg/cm ² G to 3 Kg/cm ² G. It was carried out in the same manner. The results are shown in Table 2. Example 28 In Example 23, 40 g of 1-hexene was used instead of 20 g of 1-butene, and the partial pressure of propylene was changed to 2.
Kg/cm ² G was changed to 1 Kg/cm ² G, hydrogen was introduced at a hydrogen partial pressure of 7 Kg/cm ² G, and the total pressure was 9 Kg/cm ²
The procedure was carried out in the same manner as in Example 23, except that propylene was continuously introduced so that G was obtained. The results are shown in Table 2. Example 29 Performed in the same manner as in Example 23 above, except that bis(pentamethylcyclopentadienyl) hafnium monochlorohydride was used instead of bis(pentamethylcyclopentadienyl) hafnium dichloride. did. The results are shown in Table 2. Example 30 Performed in the same manner as in Example 23 above, except that bis(pentamethylcyclopentadienyl) zirconium trichloride was used instead of bis(pentamethylcyclopentadienyl) hafnium dichloride. did. The results are shown in Table 2.

[Table] Example 31 Add 400 toluene to an autoclave with an internal volume of 1.
ml, 6 mmol of the methylaluminoxane obtained in Example 1 in terms of aluminum equivalent, and 0.01 mmol of bis(pentamethylcyclopentadienyl) hafnium dichloride were added in sequence, and the mixture was heated at 50°C.
The temperature rose to . Next, hydrogen was introduced into the autoclave so that the hydrogen partial pressure became 1 Kg/cm ² G, and propylene was further introduced continuously to bring the propylene partial pressure to 8.
The reaction was carried out for 4 hours at a temperature of 50° C. while maintaining the pressure at Kg/cm ² G. After the reaction is complete, the product is deashed using 150 ml of 3N hydrochloric acid to form a mixture of propylene-based low polymers.
181.7g was obtained. As a result of analysis of the obtained mixture of propylene-based low polymers, it was found that the amount of dimer was 64.7 g, the trimer was 58.7 g, and the amount of tetramer or higher low polymer was 58.3 g, and the average degree of polymerization was 3.1. Ta. In addition, the obtained mixture of propylene-based low polymers was analyzed by infrared absorption spectroscopy and
As a result of ¹ HNMR (270MHz) spectrum analysis, it was found that it is a propylene-based low polymer with a vinyl group at the molecular end (absorption peaks: 1640 cm ^-1 , 994 cm ^-1 , 912 cm
^-1 ) is a propylene-based low polymer with a content of 98% and a vinylidene group at the end of the molecule (absorption peak;
884 cm ^-1 ) was 2%. Further, as a result of analysis of the dimer, it was found that 4-methyl-pentene-1 was the main component, and the selectivity was 99%. The results are shown in Table 3. Example 32 In Example 31 above, the amount of toluene used was
The procedure was the same as in Example 31 except that the volume was changed from 400 ml to 200 ml, the amount of bis(pentamethylcyclopentadienyl) hafnium dichloride used was changed from 0.01 mmol to 0.005 mmol, and the polymerization time was changed from 4 hours to 8 hours. It was carried out. The results are shown in Table 3. Example 33 In Example 31, 6 mmol (aluminum equivalent) of methylaluminoxane was substituted for 6 mmol (aluminum equivalent) of methylaluminoxane.
Example 31 was carried out in the same manner as in Example 31, except that a mixture of 6 mmol of trimethylaluminum and 6 mmol of trimethylaluminum was used, and the polymerization time was changed from 8 hours to 12 hours. The results are shown in Table 3. Examples 34 to 38 Examples 34 to 38 were conducted in the same manner as in Example 31, except that the hydrogen partial pressure, polymerization temperature, and polymerization time were changed as shown in Table 3. The results are shown in Table 3. Example 39 The same procedure as in Example 31 was carried out except that hexane was used instead of toluene. The results are shown in Table 3. Example 40 In Example 31, bis(pentamethylcyclopentadienyl) hafnium dichloride was replaced with bis(pentamethylcyclopentadienyl).
The same procedure as in Example 31 was carried out except that zirconium dichloride was used. The results are shown in Table 3.

【table】

[Table] Examples 41 to 44 Add 400 toluene to an autoclave with an internal volume of 1.
ml, obtained by reacting 6 mmol of the methylaluminoxane obtained in Example 1 above in terms of aluminum equivalent, and equimolar amounts of bis(pentamethylcyclopentadienyl) hafnium dichloride and the electron-donating compound shown in Table 4. reaction product
0.01 mmol (calculated as hafnium atoms) was added one after another, and the temperature was raised to 55°C. Next, hydrogen was introduced into the autoclave so that the hydrogen partial pressure became 3 kg/cm ² G, and propylene was further introduced continuously to bring the propylene partial pressure to 6 kg/cm 2 G.
The reaction was carried out at a temperature of 55° C. for 8 hours while maintaining the pressure at Kg/cm ² G. After the reaction was completed, the product was deashed using 150 ml of 3N hydrochloric acid to obtain a mixture of propylene-based low polymers. The resulting mixture of propylene-based low polymers was analyzed. The results are shown in Table 4.

[Table] [Effects of the Invention] According to the present invention, a propylene low polymer mixture having a degree of polymerization of 2 to 10 and having a vinyl group at the molecular end or a low polymer mixture of propylene and an olefin other than propylene can be used. It can be produced with high selectivity. Therefore, according to the present invention, a propylene-based low polymer having a vinyl group at the molecular end or a low polymer of propylene and an olefin other than propylene, which is highly useful industrially, can be efficiently produced. A novel method for producing a low polymer can be provided.

[Brief explanation of the drawing]

FIG. 1 is a flow chart showing the method of the present invention.

[Claims]

1 When producing ethylene by dehydration reaction of ethanol using a tubular externally heated reactor filled with a solid catalyst, raw ethanol is introduced from the bottom of the reactor so that the raw ethanol forms an upward flow in the reactor. When the catalyst activity decreases, the catalyst with decreased activity is taken out from the top of the reactor, and the catalyst with no decrease in activity is left in the reactor, and then the newly prepared catalyst or catalyst is removed from the top of the reactor. A method for dehydrating ethanol, which comprises replenishing the regenerated catalyst and then carrying out the next dehydration reaction of ethanol. 2. When removing a catalyst with decreased activity from the reactor and replenishing the reactor with a newly prepared or regenerated catalyst, make sure to keep the catalyst in the reactor with no decrease in activity under an inert gas atmosphere. A method according to claim 1, characterized in: 3. When the catalyst activity decreases due to the dehydration reaction of ethanol, the catalyst can be treated with inert gas or steam at a temperature of 300 to 600°C in the reactor after the reaction has stopped to remove the unresidues attached to the catalyst. At least a portion of the identified substance is removed and the less active catalyst is removed from the reactor and freshly prepared.

Claims (1)

1. A method for producing a propylene-based low polymer, the method comprising using a propylene-based low polymer. 3. A method for producing a propylene-based low polymer by reacting propylene alone or propylene with an olefin other than propylene using a catalyst comprising a transition metal compound component and an organometallic compound component, in which the transition metal compound Using an alkyl-substituted cyclopentadienyl compound of zirconium and/or hafnium as a component,
and a propylene system characterized by carrying out low polymerization of propylene or low polymerization of propylene and an olefin other than propylene in the presence of hydrogen using a condensation product of an organoaluminum compound and water as the organometallic compound component. Method for producing low polymers. 4. A method for producing a propylene-based low polymer by reacting propylene alone or propylene with an olefin other than propylene using a catalyst comprising a transition metal compound component and an organometallic compound component, in which the transition metal compound In the presence of hydrogen, an alkyl-substituted cyclopentadienyl compound of zirconium and/or hafnium and an electron-donating compound are used as components, and a condensation product of an organoaluminum compound and water is used as the organometallic compound component. A method for producing a propylene-based low polymer, which comprises performing low polymerization of propylene or low polymerization of propylene and an olefin other than propylene.