JP2732346B2 - Method for producing propylene-based low polymer - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a raw material for a polymer ,
The present invention relates to a method for producing a propylene-based low polymer used as a base material used for preparing a lubricating oil, a base material used for preparing a cosmetic, a raw material for producing various chemical products, and the like. More specifically, the present invention relates to a method for producing a low polymer of a propylene having 4 to 16 carbon atoms and an α-olefin having a vinyl group at a molecular end , which has a degree of polymerization of 2 to 10 and is liquid at ordinary temperature . [0002] In general, it is known to use a Ziegler-Natta catalyst in addition to a solid catalyst containing an alkali metal for producing a propylene-based low polymer. It is known that propylene is polymerized using a sodium-potassium catalyst, a catalyst comprising a combination of a nickel compound and an aluminum compound, or a catalyst comprising a titanium compound and an organoaluminum compound. [0003] However, the products obtained by these conventional methods are low-polymers having a vinyl group at the molecular terminal.
In addition, 2-methylpentene-2,4-methylpentene-2,2,3-dimethyl-2-butene, various internal olefins, including dimers such as hexene -2 further 2
A mixture of various compounds such as vinylidene compounds including dimers such as -methylpentene-1 and 2,3-cimethylbutene-1. [0004] Accordingly, in order to obtain a propylene-based low polymer having a vinyl group at the molecular end which is industrially useful, a complicated separation operation is required, and a vinyl group at the molecular end is required. However, there is a problem in that the selectivity itself of the propylene-based low polymer having the above is low. [0005] In particular, propylene and α having 4 to 16 carbon atoms
-Regarding the low polymerization with olefin, no conventional method has been found. For example, it is possible to obtain 4-methylhexene-1 from propylene and 1-butene, or to obtain propylene and hexene-
A method for obtaining 4-methyloctene-1 from 1 is not known. [0006] The present invention has been made based on the above circumstances. That is, an object of the present invention is to have a degree of polymerization of 2 to 10 and a liquid state at normal temperature.
It is an object of the present invention to provide a method for producing a propylene-based low polymer, which has a vinyl group at a molecular terminal and can selectively produce a low polymer with propylene or an α-olefin having 4 to 16 carbon atoms such as propylene. . Means for Solving the Problems [0007] The present inventors have achieved the above object.
As a result of various investigations to achieve the, specific chemical structure
Using a catalyst consisting of a combination of organometallic compounds having
By selecting one of the appropriate reaction conditions, the degree of polymerization having high industrial utility is 2 to 10, and it is liquid at room temperature.
Having a vinyl group at the molecular end there, found that it is possible to manufacture better select housing a low polymer of propylene with carbon number 4 to 16 of the α- olefin, the completion of the present invention
Reached . That is, the present invention relates to zirconium and
Pentaalkylcyclopentadie of hafnium
Condensation of an organoaluminum compound with water
In the presence of a catalyst consisting of
In the presence, at a temperature of 20 to 80 ° C. and 10 kg / cm ² G or less
Under the following pressure conditions, propylene and C 4-16
With an α-olefin having a degree of polymerization of 2 to 10.
And is liquid at room temperature and has a vinyl group at the molecular end
A method for producing a propylene-based low polymer characterized by producing a propylene-based low polymer. Hereinafter, the method of the present invention will be described in detail. Zirconium <br/> beam or penta-alkyl cyclopentadienyl compound of hafnium is used as a catalyst component in the present invention are those represented by the following formula. _{(R 5 C 5) m ·} M · X 4- m ............... [1] [wherein, R shows an alkyl group having 1 to 20 carbon atoms, M represents a zirconium atom or a hafnium atom, X represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a halogen atom. M indicates a real number of 2 to 4. Specific examples of the alkyl group represented by R or X in the above formula [1] include a methyl group, an ethyl group,
Propyl, isopropyl, butyl, isobutyl, amyl, hexyl, heptyl, octyl,
Nonyl, capryl, undecyl, lauryl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, stearyl, nonadecyl, eicosyl and the like. As the halogen atom, chlorine atom is preferred. Specific examples of the zirconium or hafnium pentaalkylcyclopentadienyl compound represented by the above formula [1] include, 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 (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 . These compounds may be used alone or in combination of two or more. The organoaluminum compound used as a raw material of the other catalyst component of the present invention is represented by the following formula:
You . Al R ₃ ... [2] Al R ₂ Y ... [3] Al ₂ R ₃ Y ₃ ... [4] [Equations [2] to [4] R is the number 1 to 1 0 a Ruki <br/> group, a cycloalkyl group or a carbon number of 3 to 10 carbon atoms atoms
6-8 is an aryl group, Y is a hydrogen atom, a halogen atom or an alkoxy group having 1 to 5 carbon atoms. Specific examples of the organoaluminum compounds represented by these formulas [2] to [4] include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tributylaluminum, triisobutylaluminum, triamylaluminum, triamylaluminum and triamylaluminum. Octyl aluminum, diethyl aluminum monochloride, diisopropyl aluminum monochloride, diisobutyl aluminum monochloride, dioctyl aluminum monochloride, ethyl aluminum sesquichloride, diethyl aluminum hydride, dimethyl aluminum ethoxide, diethyl aluminum methoxide, and the like. Among these compounds, trialkylaluminums such as trimethylaluminum and triethylaluminum are particularly preferred. In addition, these compounds
It may be used singly or may be used in combination of two or more. [0013] For the condensation reaction between the organoaluminum compound and water, if carried out according to known techniques
No. That is, the organic aluminum compound is directly
In may be caused to react with water, it may be reacted with water of crystallization in the hydrated salt. Like this
Aluminoxanes is a condensation reaction product obtained Te, methyl aluminoxane, ethyl aluminoxane, propyl aluminoxane, isopropyl aluminoxane,
Butylaluminoxane, isobutylaluminoxane, amylaluminoxane and the like. And this a
The molecular weight of luminoxane is not particularly limited. further,
The preparation of this aluminoxane consists of propylene and α-olefin.
May be prepared prior to the low polymerization reaction with
Alternatively, it may be prepared in a reactor for performing the low polymerization reaction . Next, in the method of the present invention, the low polymerization reaction
The α-olefin used in the reaction has 4 to 16 carbon atoms.
For example, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene,
- nonene, 1-decene, 1-undecene, 1-Todesen, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-Hekisadese down, 4 - methyl-1-pentene,
Neohexane, vinylcyclohexane, 4-vinylcyclohexene and the like can be mentioned. Among these α-olefins, 1-butene, 1-pentene, 1-hexene,
Heptene and 1-octene are particularly preferred. The ratio of propylene to α-olefin used in the above-mentioned low polymerization reaction depends on the desired low polymerization rate.
It may be appropriately selected so as to conform to the composition of the coalescence, but in order to improve the selectivity of the propylene-based low polymer having a molecular terminal vinyl group, it is desirable to increase the use ratio of this propylene. In the present invention, the conditions for the low polymerization reaction with propylene and the above-mentioned α-olefin are as follows.
Adjust within the range of 0 to 80 ° C. The reaction temperature is 20 ° C
If it is lower than the lower limit, the degree of polymerization of the resulting low polymer increases and the
The yield of α-olefins that are liquid at room temperature is low.
Down. When the reaction temperature is higher than 80 ° C.,
The proportion of low-polymer low-polymers increases,
Suitable for purposes such as base materials for preparing oils and cosmetics
You won't get anything . The reaction pressure is 10 kg / c
It is important to be less than m ² G,
In a reaction under pressure, the degree of polymerization of the low polymer formed is high.
Too much . [0017] As reaction system <br/> of the low polymerization reaction in the present invention, a solution polymerization method, bulk polymerization method, but may employ any method of gas phase polymerization, solvent solution polymerization method is suitable ing. Solvents suitable for the solution polymerization include benzene, toluene, xylene, ethylbenzene, cumene, mesitylene, naphthalene, tetralin, butylbenzene,
aromatic hydrocarbons such as p-cymene, cyclohexylbenzene, diethylbenzene, benzylbenzene, dipentylbenzene, dodecylbenzene, biphenyl, 2-methylbutane, hexane, 2-methylpentane, 2,2-dimethylbutane, 2,3-dimethyl Aliphatic hydrocarbons such as butane, heptane, octane, 2,2,3-trimethylpentane, isooctane, nonane, 2,2,5-trimethylhexane, decane and todecane; cyclopentane;
In addition to alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, ethylcyclohexane and decalin, petroleum ether, petroleum benzine, petroleum naphtha, ligroin, industrial gasoline, kerosene and the like can be mentioned. The propylene of the present invention and the α-olefin
The conditions of low polymerization reaction, further studies as a result, the original of the reaction conditions, further carry out the oligomerization reaction in the presence of hydrogen gas, it was found that the polymerization activity is improved. This place
In this case , surprisingly, even if hydrogen gas is present during the low polymerization reaction , the conversion of the raw material and the α-olefin as the product does not proceed, and the conversion is improved . here
The amount of hydrogen gas introduced into this reaction system depends on the reaction system
It is preferable to use within a range of 1 to 100 mol, preferably 2 to 50 mol, based on the amount of propylene to be introduced into the solvent. The kind of the propylene-based low polymer obtained by the method of the present invention and the production ratio thereof are controlled by adjusting the kind of the raw material α-olefin, the supply ratio of propylene to α-olefin, and the reaction conditions. Various adjustments can be made by selecting . The propylene-based low polymer obtained by the method of the present invention can be suitably used for applications such as a raw material for chemical synthesis, a raw material for producing synthetic resin, a base material for preparing lubricating oil and cosmetics, and the like. Next, the present invention will be described in more detail with reference to examples and comparative examples of the present invention. Example 1 (1) Preparation of Aluminum Catalyst Component In a reaction vessel, 200 ml of toluene was added, and 47.4 ml (492 mmol) of triethylaluminum and copper sulfate pentahydrate (Cu ₂ SO ₄ .5H ₂ ) were added. O) 35.5
g (142 mmol) and add 2 g under a stream of argon.
The reaction was performed at 0 ° C. for 24 hours. Copper sulfate was filtered off from the obtained reaction solution, and toluene was distilled off to obtain 12.4 g of methylaluminoxane. The thus obtained methylaluminoxane had a molecular weight of 721 as measured by the freezing point depression method of benzene. (2) Low polymerization of propylene and α-olefin
ml, 6 mmol of the methylaluminoxane obtained in the above (1) in an aluminum equivalent, and 0.0 of bis (pentamethylcyclopentadienyl) hafnium dichloride.
1 mmol was added sequentially, and the temperature was raised to 50 ° C. Then, 20 g of 1-butene and propylene were introduced into the autoclave, and the reaction was carried out for 4 hours in a closed system at a temperature of 50 ° C. while maintaining the partial pressure of propylene at 2 kg / cm ² G. . After completion of the reaction, the product was treated with 3N hydrochloric acid (1N).
Decalcification was performed using 50 ml to obtain 16.7 g of an oligomer. For the obtained oligomer, ¹ HNMR (270 M
Hz), the content of the low polymer having a vinyl group at the molecular terminal was 79%, and the content of the low polymer having a vinylidene group at the molecular terminal was 21%.
Met. Table 1 shows the measurement results of the physical properties of this oligomer . Example 2 In Example 1, the amount of 1-butene was changed from 20 g to 40 g, and the partial pressure of propylene was changed to 2 kg / cm ² G.
To 5 kg / cm ² G, and hydrogen gas was introduced so that the partial pressure thereof became 1 kg / cm ² G, and the other operations were carried out in the same manner as in Example 1 to obtain an oligomer. Got
Table 1 shows the measurement results of the physical properties of the oligomer . Example 3 In Example 1, the partial pressure of propylene was changed to 2 kg / c.
with changing from m ² G in 6.5Kg / cm ² G, except that the propylene so as to maintain continuously introduced at a total pressure 9Kg / cm ² G, was performed in the same manner as in Example 1. Table 1 shows the measurement results of physical properties of the obtained oligomer . Example 4 In Example 1, 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. Other than that, it carried out similarly to Example 1. Obtained ori
Table 1 shows the measurement results of the physical properties of the sesame . Example 5 In Example 1, 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. Other than that, it carried out similarly to Example 1. Obtained ori
Table 1 shows the measurement results of the physical properties of the sesame . Example 6 In Example 1, 40 g of 1-hexene was used instead of 20 g of 1-butene, and the partial pressure of propylene was changed from 1 kg / cm ² G to 3 kg / cm ² G.
Hydrogen gas with its partial pressure is introduced so that the 7 Kg / cm 2 ^G, except that the total pressure was continuously introduced into the propylene so as to 9Kg / cm 2 ^G is carried out in the same manner as in Example 1 did. Table 1 shows the measurement results of physical properties of the obtained oligomer . Example 7 The procedure of Example 1 was repeated except that bis (pentamethylcyclopentadienyl) hafnium monochloride was used instead of bis (pentamethylcyclopentadienyl) hafnium dichloride used in Example 1. The procedure was performed in the same manner as in Example 1. Table 1 shows the measurement results of physical properties of the obtained oligomer . Example 8 Example 1 was repeated except that bis (pentamethylcyclopentadienyl) hafnium dichloride used in Example 1 was replaced with bis (pentamethylcyclopentadienyl) zirconium dichloride. It carried out similarly to. Table 1 shows the measurement results of physical properties of the obtained oligomer . [Table 1] According to the present invention, propylene and a α-olefin having 4 to 16 carbon atoms which have a degree of polymerization of 2 to 10, are liquid at ordinary temperature and have a vinyl group at a molecular terminal, and Can be produced with high selectivity. Therefore, the raw materials for chemical synthesis and synthetic resin
Material, base material for preparing lubricants and cosmetics, etc.
A method for efficiently producing the low polymer having high usability can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flowchart illustrating a method of the present invention.

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Claims (1)

(57) [Claims] Zirconium and / or hafnium pentaa
Alkyl cyclopentadienyl compound and organic aluminum
In the presence of a catalyst consisting of a condensation product of
Temperature of 0 to 80 ° C. and pressure of 10 kg / cm ² G or less
Propylene and α-ole having 4 to 16 carbon atoms
Fin, and the degree of polymerization is 2 to 10;
Propylene with a vinyl group at the molecular end
A method for producing a propylene-based low polymer, comprising producing a propylene-based low polymer. 2. Zirconium and / or hafnium pentaa
Alkyl cyclopentadienyl compound and organic aluminum
Catalyst Containing Condensation Product of Water Compound and Water and Hydrogen
In the presence of gas, at a temperature of 20 to 80 ° C. and 10 kg / cm
Under pressure conditions of ² G or less, propylene and carbon number 4
And an α-olefin having a polymerization degree of 2-1.
0, liquid at room temperature, and a vinyl group
A method for producing a propylene-based low polymer, comprising producing a propylene-based low polymer having the following .