JP2019094361A - Solid catalyst component for olefin polymerization, method for producing the same, catalyst for olefin polymerization, and method for producing olefin polymer - Google Patents

Abstract

[PROBLEMS] To produce a propylene homopolymer having a low melting point of less than 160 ° C., a high degree of stereoregularity and an excellent melt tension without a coexistence of α-olefins other than propylene such as ethylene with high polymerization activity. PROBLEM TO BE SOLVED: To provide a solid catalyst component for polymerization of olefins, a first step of contacting and reacting a magnesium compound, a titanium halide compound and a first internal electron donating compound, and then washing, Contacting the product with 0.001 to 0.1 mol of a second internal electron donating compound per 1 mol of magnesium atom contained in the magnesium compound in the presence of a hydrocarbon solvent; A second step of removing the solvent, a third step of washing at least once with an organic solvent containing a titanium halide in an amount of more than 5% by volume and 50% by volume or less, and Sequentially applying a fourth step of cleaning one or more times with an organic solvent containing no halogen compound are obtained, olefin polymerization solid catalyst component. [Selection diagram] None

Description

  The present invention relates to a solid catalyst component for olefins polymerization, a method for producing a solid catalyst component for olefins polymerization, a catalyst for olefins polymerization and a method for producing olefins polymer.

  Conventionally, as a catalyst for olefins polymerization, a solid catalyst comprising a transition metal catalyst component such as titanium and a typical metal catalyst component such as aluminum is widely known.

  In the polymerization of olefins such as propylene, a solid catalyst component is known which contains a magnesium atom, a titanium atom, a halogen atom and an electron donor as essential components. In addition, many methods for polymerizing or copolymerizing olefins in the presence of the catalyst for olefins polymerization comprising the solid catalyst component, the organoaluminum compound and the organosilicon compound have been proposed (for example, Patent Document 1 and Patent Document) 2).

Japanese Patent Application Laid-Open No. 11-106434 WO 2013/027560 specification

  In Patent Document 1 (Japanese Patent Application Laid-Open No. 11-106434), propylene and an α-olefin other than propylene such as ethylene are copolymerized using a solid catalyst component to produce a propylene-based random copolymer. The propylene random copolymer which has been tried and obtained as described above is said to tend to have a lower melting point as the ratio of ethylene in the copolymer is higher.

  However, when a propylene-based random copolymer is produced by the method described in Patent Document 1, the melting point of the copolymer obtained decreases as the ethylene content in the copolymer increases, but the composition distribution becomes broader, In addition, so-called polyethylene sites (portions where ethylene is continuously polymerized) are easily formed in the polymer molecular chain, and it is difficult to obtain a propylene random copolymer having a low ethylene dispersibility and a homogeneous composition, It has been found that such copolymer compositions having low ethylene dispersibility have a large amount of stickiness at the time of molding when used for film production, and the blocking resistance tends to decrease.

  On the other hand, as in Patent Document 2 (WO 2013/027560), internal electron donor compounds selected from magnesium compounds, tetravalent titanium halogen compounds and phthalic acid diesters are obtained by bringing them into contact with each other. A solid catalyst component for olefin polymerization, an organoaluminum compound and an organosilicon compound obtained by bringing an internal electron donating compound selected from malonic acid diesters into contact with the above solid component is proposed. A method for polymerizing olefins using the polymerization catalyst is proposed, and olefin polymers obtained from such a solid catalyst component have high fluidity (MFR) of molten polymer, and in particular, large-sized molding by injection molding or the like It is said to be useful in the manufacture of goods.

  However, when examined by the present inventors, when the solid catalyst component described in Patent Document 2 is polymerized under the condition that the melting point of the obtained homopolypropylene is 157 to 160 ° C., the steric properties of the obtained homopolypropylene It turned out that not only NMR-mmmm which shows regularity falls to less than 91%, but there is still room for improvement in terms of melt tension and surface stickiness at the time of using for film manufacture, and blocking resistance.

  Under such circumstances, a propylene homopolymer (homopolypropylene) having a low melting point of less than 160 ° C. and a high degree of stereoregularity and excellent melt tension even without coexistence of an α-olefin other than propylene such as ethylene is obtained. A solid catalyst component for olefins polymerization which can be produced under high polymerization activity, a method for producing a solid catalyst component for olefins polymerization, a catalyst for olefins polymerization and a method for producing olefin polymers have been required.

  Under these circumstances, the inventors of the present invention conducted intensive studies to solve the above problems, and as a result, after contacting and reacting a magnesium compound, a titanium halogen compound, and a first internal electron donor compound. The first step of washing, relative to the product obtained, 0.001 to 0.1 mol of the second internal electron donor compound per mol of magnesium atom contained in the magnesium compound in the presence of a hydrocarbon solvent A second step of removing the hydrocarbon solvent after contacting and reacting down, a third step of washing once or more with an organic solvent containing more than 5% by volume and 50% by volume or less of a titanium halogen compound, and titanium The above technical problems can be solved by the solid catalyst component for olefins polymerization formed by sequentially applying the fourth step of washing one or more times with an organic solvent containing no halogen compound. Heading, which resulted in the completion of the present invention.

That is, the present invention
(1) A first step of washing after contacting, reacting a magnesium compound, a titanium halogen compound, and a first internal electron donor compound,
After contacting and reacting a 0.001 to 0.1 mole of a second internal electron donor compound per mole of magnesium atom contained in the magnesium compound with the obtained product in the presence of a hydrocarbon solvent A second step of removing the hydrocarbon solvent,
A third step of washing one or more times with an organic solvent containing more than 5% by volume and 50% by volume or less of a titanium halogen compound and a fourth step of washing one or more times with an organic solvent not containing a titanium halogen compound A solid catalyst component for olefins polymerization characterized by
(2) The first internal electron donating compound or the second internal electron donating compound may be phthalic acid diester, malonic acid diester, maleic acid diester, succinic acid diester, alkoxyalkyl ester, cyclohexene dicarboxylic acid diester and cyclohexanedicarboxylic acid The solid catalyst component for olefin polymerization according to the above (1), which is one or more selected from acid diesters,
(3) The first internal electron donor compound is one or more selected from phthalic acid diester, cyclohexene dicarboxylic acid diester and cyclohexane dicarboxylic acid diester, and the second internal electron donor compound is phthalic acid diester, malon The solid catalyst component for olefin polymerization according to the above (1), which is one or more selected from acid diesters, maleic acid diesters, succinic acid diesters, alkoxyalkyl esters, cyclohexene dicarboxylic acid diesters and cyclohexane dicarboxylic acid diesters,
(4) The first internal electron donor compound is one or more selected from di-n-butyl phthalate and diisobutyl phthalate, and the second internal electron donor compound is di-n-butyl phthalate And a solid catalyst component for polymerizing olefins according to the above (1), which is one or more selected from phthalic acid diesters other than diisobutyl phthalic acid and malonic acid diesters,
(5) A first step of bringing a magnesium compound, a titanium halogen compound, and a first internal electron donor compound into contact with each other, reacting them, and then washing them;
After contacting and reacting a 0.001 to 0.1 mole of a second internal electron donor compound per mole of magnesium atom contained in the magnesium compound with the obtained product in the presence of a hydrocarbon solvent A second step of removing the hydrocarbon solvent,
A third step of washing one or more times with an organic solvent containing more than 5% by volume and 50% by volume or less of a titanium halogen compound and a fourth step of washing one or more times with an organic solvent not containing a titanium halogen compound A process for producing a solid catalyst component for olefins polymerization characterized by
(6) The first internal electron donating compound or the second internal electron donating compound is phthalic acid diester, malonic acid diester, maleic acid diester, succinic acid diester, alkoxyalkyl ester, cyclohexene dicarboxylic acid diester and cyclohexane The method for producing a solid catalyst component for olefins polymerization according to the above (5), which is one or more selected from dicarboxylic acid diesters,
(7) The first internal electron donor compound is one or more selected from phthalic acid diester, cyclohexene dicarboxylic acid diester and cyclohexane dicarboxylic acid diester, and the second internal electron donor compound is phthalic acid diester, malon The method for producing a solid catalyst component for olefins polymerization according to the above (5), which is one or more selected from acid diesters, maleic acid diesters, succinic acid diesters, alkoxyalkyl esters, cyclohexene dicarboxylic acid diesters, and cyclohexane dicarboxylic acid diesters,
(8) The first internal electron donor compound is one or more selected from dibutyl phthalate and diisobutyl phthalate, and the second internal electron donor compound is phthalate. The method for producing a solid catalyst component for olefins polymerization according to the above (5), which is one or more selected from phthalic acid diesters other than di-n-butyl acid and diisobutyl phthalic acid and malonic acid diesters,
(9) (I) The solid catalyst component for olefins polymerization according to any one of the above (1) to (4), and (II) the following general formula (1):
R ¹ _p AlQ _3-p (1)
(In the formula, R ¹ is an alkyl group having 1 to 6 carbon atoms, Q is a hydrogen atom or a halogen atom, p is 0 <a real number of p ≦ 3, each of R ¹ when R ¹ existing in plural numbers Olefins characterized in that they may be the same or different, and when there are a plurality of Q, each Q may be the same or different) and is brought into contact with an organoaluminum compound Polymerization catalyst,
(10) The catalyst for olefins polymerization according to the above (9), which is further contacted with (III) an external electron donating compound,
(11) The (III) external electron donating compound is a compound represented by the following general formula (2):
R ² _q Si (OR ³ ) _4-q (2)
(Wherein R ² represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a phenyl group, a vinyl group, an allyl group, an aralkyl group, an alkylamino group having 1 to 12 carbon atoms, or carbon When it is a dialkylamino group of the number 1 to 12, and a plurality of R ² are present, each R ² may be the same or different.R ³ is an alkyl group having 1 to 4 carbon atoms, 3 carbon atoms 6 cycloalkyl group, a phenyl group, a vinyl group, an allyl group or an aralkyl group, if R ³ there are a plurality each R ³ may be different even in the same .q is 0 ≦ q ≦ It is an integer of 3.)
The catalyst for olefins polymerization according to the above (10), which is one or more organosilicon compounds selected from
(12) A process for producing an olefin polymer comprising polymerizing olefins in the presence of the catalyst for olefins polymerization according to any one of (9) to (11) above,
(13) The method for producing an olefin polymer according to the above (12), wherein the olefin is propylene, and (14) the obtained olefin polymer has a melt flow rate of 1.0 kg / 10 minutes or more, and a melting point (12) or (13), wherein the isotactic pentad fraction in the range of 157 to 160 ° C. is 91.0% or more,
To provide

  According to the present invention, a propylene homopolymer (homopolypropylene) having a low melting point of less than 160 ° C. and a high degree of stereoregularity and excellent melt tension even without coexistence of an α-olefin other than propylene such as ethylene It is possible to provide a solid catalyst component for olefins polymerization which can be produced under high polymerization activity, a method for producing a solid catalyst component for olefins polymerization, a catalyst for olefins polymerization and a method for producing olefin polymers.

First, the solid catalyst component for olefins polymerization according to the present invention is obtained by the first step of washing after contacting, reacting a magnesium compound, a titanium halogen compound, and a first internal electron donor compound. The product is contacted and reacted with 0.001 to 0.1 mol of a second internal electron donor compound per mol of magnesium atom contained in the magnesium compound in the presence of a hydrocarbon solvent, and then the hydrocarbon is reacted. Second step of removing hydrogen solvent, third step of washing one or more times with an organic solvent containing more than 5% by volume and 50% by volume or less of a titanium halogen compound, and one or more times with an organic solvent not containing a titanium halogen compound It is characterized in that the fourth step of cleaning is sequentially performed.
Since the solid catalyst component for olefins polymerization according to the present invention is represented by the method for producing such a solid catalyst component, the details of the production method and the like will be described below.

In the solid catalyst component for olefins polymerization according to the present invention, the magnesium compound may be selected from magnesium dihalide, dialkylmagnesium, alkylmagnesium halide, dialkoxymagnesium, diaryloxymagnesium, halogenated alkoxymagnesium, fatty acid magnesium etc. One or more can be mentioned.
Among these magnesium compounds, dialkoxymagnesium is preferable, and specific examples thereof include dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, ethoxymethoxymagnesium, ethoxypropoxymagnesium, butoxyethoxymagnesium, etc. Magnesium is particularly preferred.
The above dialkoxymagnesium may be obtained by reacting metal magnesium with an alcohol in the presence of a halogen or a halogen-containing metal compound or the like.
The magnesium compounds may be used alone or in combination of two or more.

Furthermore, as the dialkoxymagnesium constituting the solid catalyst component for olefins polymerization according to the present invention, granular or powdery ones are preferable, and particles having an irregular or spherical particle shape are suitable.
For example, when the magnesium compound is spherical dialkoxymagnesium, a polymer powder having a better particle shape (more spherical) and a narrow particle size distribution can be easily obtained, and the polymer powder produced during the polymerization operation The handling operability of the present invention can be improved, and clogging of the pipe caused by the fine powder contained in the produced polymer powder can be easily suppressed.

The spherical dialkoxymagnesium does not necessarily have to be a true spherical shape, and includes an elliptical shape or a potato shape, and specifically, the circularity determined by the shape of the particle from the area S and the peripheral length L of the particle Is suitably 3 or less, more preferably 1 or 2 and even more preferably 1 to 1.5.
In the present application document, the degree of circularity of dialkoxymagnesium is obtained by photographing 500 or more pieces of dialkoxymagnesium particles with a scanning electron microscope, and processing the photographed particles with image analysis processing software to obtain the area S of each particle. And the circumferential length L, and the circularity of each dialkoxy magnesium particle is expressed by the following equation: Circularity of each dialkoxy magnesium particle = L ² ÷ (4π × S)
Means the arithmetic mean value when calculated by the above, and the degree of circularity shows a value closer to 1 as the shape of the particle approaches a true circle.

The magnesium compound preferably has an average particle diameter of 1 to 200 μm, and more preferably 5 to 150 μm.
When the magnesium compound is spherical dialkoxymagnesium, the average particle diameter thereof is preferably 1 to 100 μm, more preferably 5 to 50 μm, and still more preferably 10 to 40 μm.

In the present application, the average particle diameter of the magnesium compound is 50% of the particle diameter of the average particle diameter D ₅₀ (the cumulative particle diameter in the volume integrated particle size distribution when measured using a laser light scattering diffraction particle sizer Means).

The magnesium compound preferably has a narrow particle size distribution with a small particle size and a small particle size.
Specifically, particles having a particle size of 5 μm or less are preferably 20% or less, and more preferably 10% or less.
On the other hand, that whose particle | grains of 100 micrometers or more are 10% or less is preferable, and what is 5% or less is more preferable.
Furthermore, its particle size distribution is ln (D ₉₀ / D ₁₀ ) (where D ₉₀ is the particle size of 90% in integrated particle size in volume integrated particle size distribution, and D ₁₀ is the particle size of 10% in integrated particle size in volume integrated particle size distribution It is preferably 3 or less, more preferably 2 or less.

  The method for producing the spherical dialkoxymagnesium described in, for example, JP-A-58-41832, JP-A-62-51633, JP-A-3-74341, JP-A-4-368391, JP-A-8- No. 73388 gazette etc. are illustrated.

  The magnesium compound is preferably in the form of a solution or a suspension at the time of reaction, and the reaction can be suitably advanced by being in the form of a solution or a suspension.

When the above magnesium compound is solid, it can be made into a solution-like magnesium compound by dissolving it in a solvent having the solubilizing ability of the magnesium compound, or it can be prepared in a solvent which does not have the solubilizing ability of the magnesium compound. By making it cloudy, it can be set as a magnesium compound suspension.
When the magnesium compound is liquid, it may be used as it is as a solution magnesium compound, or may be used as a solution magnesium compound by further dissolving it in a solvent having the solubilizing ability of the magnesium compound. .

In the solid catalyst component for olefins polymerization according to the present invention, the titanium halogen compound is not particularly limited, but the following general formula (3)
Ti (OR ⁴ ) _r X _4-r (3)
(Wherein, R ⁴ represents an alkyl group having 1 to ⁴ carbon atoms, X represents a halogen atom such as chlorine atom, bromine atom, iodine atom, and r is an integer of 0 or 1 to 3). It is preferable that it is one or more compounds selected from the group of titanium halides or alkoxy titanium halides.

Examples of titanium halides include titanium tetrahalides such as titanium tetrachloride, titanium tetrabromide and titanium tetraiodide.
Further, as alkoxytitanium halide, methoxytitanium trichloride, ethoxytitanium trichloride, propoxytitanium trichloride, n-butoxytitanium trichloride, dimethoxytitanium dichloride, diethoxytitanium dichloride, dipropoxytitanium dichloride, di-n-butoxytitanium One or more selected from dichloride, trimethoxy titanium chloride, triethoxy titanium chloride, tripropoxy titanium chloride, tri-n-butoxy titanium chloride and the like can be mentioned.
The titanium halogen compound is preferably titanium tetrahalide, more preferably titanium tetrachloride.
These titanium halogen compounds can be used alone or in combination of two or more.

  Examples of the first internal electron donating compound include one or more selected from phthalic acid diesters, malonic acid diesters, maleic acid diesters, succinic acid diesters, alkoxyalkyl esters, cyclohexene dicarboxylic acid diesters and cyclohexane dicarboxylic acid diesters.

  The first internal electron donating compound is preferably one or more selected from phthalic acid diesters, malonic acid diesters, alkyl substituted malonic acid diesters, maleic acid diesters, succinic acid diesters, cyclohexene dicarboxylic acid diesters and cyclohexane dicarboxylic acid diesters. And more preferably one or more selected from phthalic acid diesters, malonic acid diesters, alkyl substituted malonic acid diesters, succinic acid diesters, cyclohexene dicarboxylic acid diesters and cyclohexane dicarboxylic acid diesters, and phthalic acid diesters, cyclohexene dicarboxylic acid diesters and cyclohexane dicarboxylic acid diesters And more preferably one or more selected from phthalic acid diesters, 1-cyclohexene-1,2-dicarboxylic acid Ester, 4-cyclohexene-1,2-dicarboxylic acid diester, and cyclohexane are more preferable one or more kinds selected from dicarboxylic acid diesters, one or more selected from phthalate -n- butyl and diisobutyl phthalate is more preferable.

  The solid catalyst component for olefins polymerization according to the present invention is formed by contacting and reacting a magnesium compound, a titanium halogen compound, and a first internal electron donating compound in the first step, and then washing them. is there.

  The contact of the magnesium compound, the titanium halogen compound and the first internal electron donating compound in the first step is preferably carried out with stirring under an inert gas atmosphere with water and the like removed. .

  The contact temperature of each component may be a relatively low temperature range around room temperature when simply contacting and stirring and mixing, or dispersing or suspending and modifying it, but it may be reacted after contact In the case of obtaining a product, 40 to 130 ° C. is preferable because reaction rate and reaction control become easy. The stirring time is preferably 1 minute or more, more preferably 10 minutes or more, and still more preferably 30 minutes or more.

The cleaning process in the first step is preferably performed using a hydrocarbon compound which is liquid at normal temperature as a cleaning agent, and as the hydrocarbon compound, it preferably contains no halogen atom and is liquid at normal temperature, Aromatic hydrocarbon compounds or saturated hydrocarbon compounds which are liquid at normal temperature are preferred.
Specifically, linear or branched aliphatic hydrocarbon compounds having a boiling point of 50 to 150 ° C. such as hexane, heptane, decane, methyl heptane etc., and alicyclic hydrocarbons having a boiling point 50 to 150 ° C. such as cyclohexane, ethylcyclohexane etc. One or more compounds selected from compounds, aromatic hydrocarbon compounds having a boiling point of 50 to 150 ° C. such as toluene, xylene, ethylbenzene and the like can be mentioned. Among the above, linear aliphatic hydrocarbon compounds having a boiling point of 50 to 150 ° C. And at least one aromatic hydrocarbon compound having a boiling point of 50 to 150 ° C., preferably an aromatic hydrocarbon compound having a boiling point of 50 to 150 ° C., and more preferably one or more selected from toluene, heptane and ethylbenzene.

0-110 degreeC is preferable, as for the temperature at the time of the washing process in a 1st process, 30-100 degreeC is more preferable, and 30-90 degreeC is further more preferable.
The amount of the washing solution used in the first step is preferably 1 to 500 mL, more preferably 3 to 200 mL, and still more preferably 5 to 100 mL per 1 g of the reaction product.
The number of times of washing in the first step may be one or more, but is preferably 1 to 20, more preferably 1 to 15, and still more preferably 1 to 10. In addition, even when the number of times of washing is multiple times, it is preferable to use the above-mentioned amount of washing liquid for each washing.

  In a particularly preferred embodiment of the first step, spherical dialkoxymagnesium is suspended in a hydrocarbon compound having a boiling point of 50 to 150 ° C., and then one or two of the first electron donor compounds are added to this suspension. After bringing the above into contact, the suspension is brought into contact with a tetravalent titanium halogen compound to carry out a reaction treatment, and the reaction product is washed with a washing liquid which is a liquid hydrocarbon compound at normal temperature. be able to.

Before or after contacting the first electron donating compound in the first step, preferably at a temperature of -20 to 70 ° C, more preferably -10 to 60 ° C, still more preferably -10 to 30 ° C The aging reaction is preferably performed for 1 minute to 6 hours, more preferably 5 minutes to 4 hours, further preferably 10 minutes to 3 hours, and then preferably 30 to 130 ° C., more preferably 40 to 120 ° C., further preferably Preferably, the reaction treatment is carried out at a temperature of 50 to 115 ° C., preferably for 0.5 to 6 hours, more preferably for 0.5 to 5 hours, and still more preferably for 1 to 4 hours.
After completion of the above reaction, the suspension after washing treatment is appropriately left standing, and the supernatant liquid is removed to make it wet (slurry) or may be dried by hot air drying or the like, or after washing treatment The remaining supernatant may not be removed, and may be subjected to the second step in the form of a suspension. When using for a 2nd process as it is in the state of a suspension, while being able to abbreviate | omit a drying process, it can abbreviate | omit adding an inert organic solvent in a 2nd process.

  The solid catalyst component for olefins polymerization according to the present invention has a second internal of 0.001 to 0.1 mol per 1 mol of magnesium atom contained in the magnesium compound with respect to the product obtained in the first step. After the electron donor compound is contacted and reacted in the presence of a hydrocarbon solvent, a second step of removing the hydrocarbon solvent is performed.

Examples of the second internal electron donor compound include the same compounds as the compounds listed above as the first internal electron donor compound, and examples thereof include phthalic acid diester, malonic acid diester, alkyl-substituted malonic acid diester, and maleic acid Examples thereof include one or more selected from diesters, succinic acid diesters, alkoxyalkyl esters, cycloalkene dicarboxylic acid diesters and cycloalkane dicarboxylic acid diesters, and phthalic acid diesters, malonic acid diesters, maleic acid diesters, succinic acid diesters, alkoxy One or more selected from alkyl esters, cycloalkene dicarboxylic acid diesters, cycloalkane dicarboxylic acid diesters and the like are preferable,
More than one selected from phthalic acid diesters, malonic acid diesters, alkyl-substituted malonic acid diesters, maleic acid diesters, succinic acid diesters, cyclohexene dicarboxylic acid diesters, etc., more preferred are phthalic acid diesters, malonic acid diesters, alkyl-substituted malonic acid diesters, One or more selected from maleic acid diesters and succinic acid diesters is more preferable, and is selected from phthalic acid diesters other than di-n-butyl phthalate and isobutyl phthalate, malonic acid diesters, alkyl-substituted malonic acid diesters and maleic acid diesters, etc. One or more is more preferable, and one or more selected from phthalic acid diesters other than di-n-butyl phthalic acid and isobutyl phthalic acid, malonic acid diesters and the like are still more preferable.

  The first internal electron donor and the second internal electron donor may be identical to or different from each other.

As a combination of the first internal electron donor and the second internal electron donor,
(1) The first internal electron donor compound is selected from phthalic acid diesters, and the second internal electron donor compounds are selected from phthalic acid diesters, malonic acid diesters, alkyl substituted malonic acid diesters, alkoxyalkyl esters and maleic acid diesters Any combination,
(2) Any combination wherein the first internal electron donor compound is selected from cyclohexene dicarboxylic acid diesters, and the second internal electron donor compounds are selected from phthalic acid diesters, malonic acid diesters and alkyl-substituted malonic acid diesters, or
(3) Any combination wherein the first internal electron donor compound is selected from cyclohexanedicarboxylic acid diester and the second internal electron donor compound is selected from phthalic acid diester, malonic acid diester and alkyl-substituted malonic acid diester,
Preferred is one selected from
(4) A combination of a first internal electron donor compound with a phthalic acid diester and a second internal electron donor compound with an alkyl-substituted malonic acid diester,
(5) A combination of a first internal electron donor compound with cyclohexene dicarboxylic acid diester, a second internal electron donor compound with an alkyl-substituted malonic acid diester, and a first internal electron donor compound with cyclohexanedicarboxylic acid diester, The combination of two internal electron donor compounds is preferably an alkyl-substituted malonic acid diester.

The contact amount of the second internal electron donor compound with respect to the product obtained in the first step is 0.001 to 0.1 mole per mole of magnesium atom contained in the above-mentioned product, It is preferable that it is 0.005-0.05 mol, and it is more preferable that it is 0.008-0.03 mol.
By setting the contact amount of the second internal electron donor compound within the above range, the formation of non-stereospecific active sites in the obtained solid catalyst component is suppressed, and the reaction in the obtained solid catalyst component Since by-products and excess titanium components are efficiently removed, when such solid catalyst components are subjected to polymerization of propylene, the stereoregularity of the obtained low melting point polypropylene can be maintained at a high level .

In the second step, the product obtained in the first step is contacted with and reacted with a second internal electron donor compound in the presence of a hydrocarbon solvent.
The contact and reaction of the product obtained in the first step with the second internal electron donor compound is preferably carried out with stirring.
In the second step, contacting the second internal electron-donating compound with the product obtained in the first step by contacting the second internal electron-donating compound in the presence of the hydrocarbon solvent. Can be improved.

As said hydrocarbon solvent used at a 2nd process, 1 or more types chosen from the hydrocarbon compound used as a washing | cleaning agent at the time of the washing process of a said 1st process can be illustrated.
The concentration of the titanium halogen compound in the hydrocarbon solvent to be contacted and reacted in the second step is particularly insofar as the adsorption of the second internal electron donor compound to the product obtained in the first step is not inhibited. Although not limiting, it is desirable to be as low as possible. In order to suppress the formation of a complex compound due to the interaction between the second internal electron donor compound and the titanium halogen compound, the concentration of the titanium halogen compound in the hydrocarbon solvent is preferably 10% by volume or less, and is 5% by volume or less Is more preferably 3% by volume or less, still more preferably 1% by volume or less.
By setting the concentration of the titanium halogen compound contained in the hydrocarbon solvent in the second step to the above range, the adsorption of the second internal electron donor compound to the product obtained in the first step is efficiently performed. The formation of non-stereospecific active sites is suppressed.
In order to control the concentration of the titanium halogen compound contained in the hydrocarbon solvent within the above range, it is preferable not to newly add the titanium halogen compound to the reaction system in the second step.

In the second step, the temperature at which the second internal electron donor compound is brought into contact and reacted is preferably 40 to 130 ° C., more preferably 60 to 120 ° C., and still more preferably 70 to 120 ° C.
When the reaction temperature is less than 40 ° C., the reaction does not proceed sufficiently, resulting in insufficient performance of the resulting solid catalyst component, and when the reaction temperature exceeds 130 ° C., evaporation of the used solvent occurs. Becomes noticeable, and it becomes difficult to control the reaction.
The time for contacting and reacting the second internal electron donor compound is preferably 1 minute or more, more preferably 3 minutes to 60 minutes, and still more preferably 5 minutes to 30 minutes.

In the second step, after the second internal electron donor compound is brought into contact and reacted, the hydrocarbon solvent is removed.
In the second step, the second internal electron donating compound is brought into contact and reacted in the presence of a hydrocarbon solvent, and then the hydrocarbon solvent is removed to facilitate impurities remaining in the reaction system. It can be removed.

  The solid catalyst component for olefins polymerization according to the present invention is subjected to the second step, and once with an organic solvent containing more than 5% by volume and 50% by volume or less of a titanium halogen compound based on the obtained product The third step of cleaning is performed.

  As specific examples of the titanium halogen compound, the same ones as exemplified in the first step can be mentioned.

The organic solvent is preferably one containing a hydrocarbon compound which is liquid at normal temperature which dissolves the titanium halogen compound, and the hydrocarbon compound which does not contain a halogen atom is preferably one which is liquid at normal temperature, and aromatic which is liquid at normal temperature Hydrocarbon compounds or saturated hydrocarbon compounds are preferred.
Specifically, linear or branched aliphatic hydrocarbon compounds having a boiling point of 50 to 150 ° C. such as hexane, heptane, decane, methyl heptane etc., and alicyclic hydrocarbons having a boiling point 50 to 150 ° C. such as cyclohexane, ethylcyclohexane etc. One or more compounds selected from compounds, aromatic hydrocarbon compounds having a boiling point of 50 to 150 ° C. such as toluene, xylene, ethylbenzene and the like can be mentioned. Among the above, linear aliphatic hydrocarbon compounds having a boiling point of 50 to 150 ° C. And at least one aromatic hydrocarbon compound having a boiling point of 50 to 150 ° C., preferably an aromatic hydrocarbon compound having a boiling point of 50 to 150 ° C., and more preferably one or more selected from toluene, heptane and ethylbenzene.

The content of the titanium halide in the organic solvent used in the third step is more than 5% by volume and 50% by volume or less, preferably 5 to 49% by volume, more preferably 5 to 45% by volume, 10 to 10%. 45% by volume is more preferred.
The titanium halogen compound in the organic solvent used in the third step is a titanium halogen compound in the organic solvent utilizing the unreacted titanium halogen compound remaining in the system after removing the hydrocarbon solvent in the second step Although the amount may be controlled, in order to control the amount of titanium halogen compounds in the organic solvent more simply, after removing the hydrocarbon solvent in the second step, titanium such as tetravalent titanium halogen compounds is newly added. It is preferred to add the halogen compound directly into the organic solvent or system.

  The activity of the catalyst can be easily controlled by controlling the content of the titanium halogen compound in the organic solvent within the above range.

80-130 degreeC is preferable, as for the temperature at the time of the washing process in a 3rd process, 90-120 degreeC is more preferable, and 100-110 degreeC is more preferable.
In the third step, the number of times of washing treatment with an organic solvent containing a titanium halogen compound is one or more, preferably two or more, more preferably 2 to 6 and even more preferably 2 to 5.
By making the frequency | count of washing | cleaning processes by the organic solvent containing a titanium halogen compound into the said range, a reaction by-product and an excess titanium component are easily removable.
In the method for producing a solid catalyst component for olefins polymerization of the present invention, the reaction product obtained in the second step may be pretreated and then subjected to the third step. It is preferable to apply the third step continuously without applying an acid.
In the case where the reaction product obtained in the second step is pretreated, for example, the product obtained by removing the organic solvent in the second step is additionally pretreated with tetravalent titanium halogen as a pretreatment. The aspect which wash-processes with a detergent in the state which added titanium halogen compounds, such as a compound etc., directly in the detergent or system inside can be mentioned. The washing in this pretreatment can be performed in the same manner as the washing in the first step.

  The solid catalyst component for olefins polymerization according to the present invention is obtained by applying the third step and then performing the fourth step of washing with an organic solvent not containing a titanium halogen compound one or more times.

As an organic solvent used at a 4th process, what consists of a hydrocarbon compound which can comprise the organic solvent used at a 3rd process is preferable, and the specific example of the said hydrocarbon compound is as having mentioned above.
In particular, as the above-mentioned hydrocarbon compound, an alicyclic hydrocarbon compound having a boiling point of 50 to 150 ° C. and a boiling point of 50 to 150 ° C. is preferable, and a linear aliphatic hydrocarbon compound having a boiling point of 50 to 150 ° C. is more preferable, hexane And heptane are more preferred.
As a method of washing with an organic solvent not containing a titanium halogen compound one or more times, after removing the supernatant after the washing treatment in the third step to make it wet (slurry), a titanium halogen compound is newly included. Method of performing washing treatment by adding no organic solvent, removing the supernatant after washing treatment in the third step and making it in a dry state, and then washing with addition of an organic solvent not containing a titanium halogen compound anew Among these, after removing the supernatant liquid after the washing treatment in the third step to make it wet (slurry), an organic solvent which does not contain a titanium halogen compound newly It is preferable to carry out the washing treatment by adding

20-80 degreeC is preferable, as for the temperature at the time of the washing process in a 4th process, 30-70 degreeC is more preferable, and 40-60 degreeC is more preferable.
In the fourth step, the number of times of washing treatment with an organic solvent not containing a titanium halogen compound is one or more, preferably two or more, more preferably 2 to 10, and still more preferably 4 to 6.

  In the third step, after the washing treatment with the organic solvent containing the titanium halogen compound is performed once or more, the washing treatment with the organic solvent not containing the titanium halogen compound is performed once or more in the fourth step. The unreacted titanium by-product, the reaction by-product and the weakly adsorbing titanium component remaining in the solid catalyst component can be efficiently removed.

  After the fourth step, the solid catalyst component can be isolated by subjecting it to solid-liquid separation treatment as appropriate.

The solid catalyst component for olefins polymerization according to the present invention preferably has a magnesium atom content of 10 to 70% by mass, more preferably 10 to 50% by mass, and more preferably 15 to 40% by mass. Is more preferable, and one having 15 to 25% by mass is more preferable.
The solid catalyst component for olefins polymerization according to the present invention preferably has a titanium atom content of 0.5 to 8.0% by mass, and preferably 1.0 to 6.0% by mass. It is more preferable that the content is 4.0 to 4.5% by mass.
The solid catalyst component for olefins polymerization according to the present invention preferably has a content of halogen atoms of 20 to 85% by mass, more preferably 30 to 80% by mass, and more preferably 40 to 75% by mass. The content is more preferably 45 to 70% by mass.
The solid catalyst component for olefins polymerization according to the present invention preferably has a content ratio of the first internal electron donating compound of 1.0 to 15.0% by mass, and preferably 3.0 to 13.0% by mass. And more preferably 5.0 to 11.0% by mass.
The solid catalyst component for olefins polymerization according to the present invention preferably has a content ratio of the second internal electron donating compound of 0.1 to 5.0% by mass, preferably 0.3 to 4.0% by mass. And more preferably 0.5 to 3.0% by mass.
The solid catalyst component for olefins polymerization according to the present invention preferably has a total content ratio of 1.1 to 20.0 mass% of the first internal electron donor and the second internal electron donor. The content of 3.3 to 17.0% by mass is more preferable, and the content of 5.5 to 14.0% by mass is more preferable.

  The solid catalyst component for olefins polymerization according to the present invention has a titanium atom content of 4 to 4.5 mass% and a magnesium atom content of 15 to 25 mass% in order to exert its overall performance in a well-balanced manner. Content of the halogen atom is 45 to 75% by mass, the content of the first internal electron donor compound is 5.0 to 11.0% by mass, and the content of the second internal electron donor compound is 0.5 What is -3.0 mass% mass% is desirable.

  According to the present invention, a propylene homopolymer (homopolypropylene) which has a melting point lower than 160 ° C. and a high degree of stereoregularity and excellent melt tension even without coexistence of an α-olefin other than propylene such as ethylene is obtained. It is possible to provide a solid catalyst component for olefin polymerization which can be produced under high polymerization activity.

Next, the method for producing the solid catalyst component for olefins polymerization according to the present invention will be described.
The process for producing a solid catalyst component for olefins polymerization according to the present invention comprises the first step of bringing a magnesium compound, a titanium halogen compound and a first internal electron donor compound into contact with each other, reacting them, and then washing them. After contacting and reacting a 0.001 to 0.1 mole of a second internal electron donor compound per mole of magnesium atom contained in the magnesium compound with the obtained product in the presence of a hydrocarbon solvent The second step of removing the hydrocarbon solvent, the third step of washing one or more times with an organic solvent containing more than 5% by volume and 50% by volume or less of a titanium halogen compound, and an organic solvent not containing a titanium halogen compound A fourth step of washing one or more times is sequentially performed.

  Details of the method for producing a solid catalyst component for olefins polymerization according to the present invention are the same as the contents described in the production method described in the description of the solid catalyst component for olefins polymerization of the present invention.

  According to the present invention, a propylene homopolymer (homopolypropylene) having a low melting point of less than 160 ° C. and a high degree of stereoregularity and excellent melt tension even without coexistence of an α-olefin other than propylene such as ethylene It is possible to provide a method for conveniently producing a solid catalyst component for olefins polymerization which can be produced under high polymerization activity.

Next, the olefin polymerization catalyst according to the present invention will be described.
The olefin polymerization catalyst according to the present invention comprises (I) a solid catalyst component for olefins polymerization according to the present invention, and (II) the following general formula (1):
R ¹ _p AlQ _3-p (1)
(In the formula, R ¹ is an alkyl group having 1 to 6 carbon atoms, Q is a hydrogen atom or a halogen atom, p is 0 <a real number of p ≦ 3, each of R ¹ when R ¹ existing in plural numbers It may be the same as or different from one another, and when there are a plurality of Q, each Q may be the same or different, and is characterized by being brought into contact with an organoaluminum compound is there.

In the organoaluminum compound represented by the general formula (II), R ¹ is an alkyl group having 1 to 6 carbon atoms, and specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group And isobutyl group.

  In the organoaluminum compound represented by the above general formula (II), Q represents a hydrogen atom or a halogen atom, and when Q is a halogen atom, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom can be mentioned.

In the organoaluminum compound represented by the formula (II), each R ¹ when R ¹ existing in plural numbers may be the same or different and each Q if Q there are a plurality may be the same It may be different.

  Specific examples of the organoaluminum compound represented by the above general formula (II) include one or more selected from triethylaluminum, diethylaluminum chloride, triisobutylaluminum, diethylaluminum bromide and diethylaluminum hydride, and triethylaluminum And triisobutylaluminum are preferred.

  The catalyst for olefins polymerization according to the present invention further comprises (III) exterior together with the solid catalyst component for olefins polymerization according to the above (I) and the organoaluminum compound represented by (II) general formula (1) It may be brought into contact with an electron donating compound.

  As such an external electron donating compound, an organic compound containing an oxygen atom or a nitrogen atom can be mentioned. Specifically, for example, alcohols, phenols, ethers, esters, ketones, acid halides, etc. Aldehydes, amines, amides, nitriles, isocyanates, organic silicon compounds, and in particular, organic silicon compounds having a Si-O-C bond and the like can be mentioned.

  Among the above external electron donor compounds, esters such as ethyl benzoate, ethyl p-methoxybenzoate, ethyl p-ethoxybenzoate, methyl p-toluylate, ethyl p-toluylate, methyl anisate, ethyl anisate, etc. , 1,3-diethers and organosilicon compounds containing Si-O-C bonds are preferred, and organosilicon compounds having Si-O-C bonds are particularly preferred.

As the above-mentioned external electron donor compound, the following general formula (2)
R ² _q Si (OR ³ ) _4-q (2)
(Wherein R ² represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a phenyl group, a vinyl group, an allyl group, an aralkyl group, an alkylamino group having 1 to 12 carbon atoms, or carbon When it is a dialkylamino group of the number 1 to 12, and a plurality of R ² are present, each R ² may be the same or different.R ³ is an alkyl group having 1 to 4 carbon atoms, 3 carbon atoms 6 cycloalkyl group, a phenyl group, a vinyl group, an allyl group or an aralkyl group, if R ³ there are a plurality each R ³ may be different even in the same .q is 0 ≦ q ≦ It is an integer of 3.)
It is preferable that it is one or more organosilicon compounds selected from

  Examples of the above organosilicon compounds include phenylalkoxysilane, alkylalkoxysilane, phenyl (alkyl) alkoxysilane, vinylsilane, allylsilane, cycloalkylalkoxysilane, cycloalkyl (alkyl) alkoxysilane, (alkylamino) alkoxysilane, alkyl (alkylamino) ) Alkoxysilane, alkyl (dialkylamino) alkoxysilane, cycloalkyl (alkylamino) alkoxysilane, (polycyclic amino) alkoxysilane, (alkylamino) alkylsilane, (dialkylamino) alkylsilane, cycloalkyl (alkylamino) alkyl Silane, (polycyclic amino) alkylsilane, etc. can be mentioned, among which di-n-propyldimethoxysilane, diisopropyldimethoxysilane Di-n-butyldimethoxysilane, diisobutyldimethoxysilane, di-tert-butyldimethoxysilane, di-n-butyldiethoxysilane, tert-butyltrimethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyldimethoxysilane, Cyclohexylmethyldiethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylethyldiethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylethyl diethoxysilane, cyclohexylcyclopentyldimethoxysilane, Cyclohexylcyclopentyldiethoxysilane, 3-methylcyclo Hexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, 3,5-dimethylcyclohexyl (cyclopentyl) dimethoxysilane, bis (ethylamino) methylethylsilane, t-butylmethylbis (ethylamino) silane, bis (ethylamino) Dicyclohexylsilane, dicyclopentylbis (ethylamino) silane, bis (methylamino) (methylcyclopentylamino) methylsilane, diethylaminotriethoxysilane, bis (cyclohexylamino) dimethoxysilane, bis (perhydroisoquinolino) dimethoxysilane, bis ( Perhydroquinolino) dimethoxysilane, ethyl (isoquinolino) dimethoxysilane, bis (methylamino) di-t-butylsilane, bis (ethyl amino) ) One or more selected from dicyclopentyl silane and bis (ethylamino) butyldiisopropylsilane are preferred.

  According to the present invention, a propylene homopolymer (homopolypropylene) having a low melting point of less than 160 ° C. and a high degree of stereoregularity and excellent melt tension even without coexistence of an α-olefin other than propylene such as ethylene It is possible to provide an olefin polymerization catalyst which can be produced under high polymerization activity.

In the olefin polymerization catalyst according to the present invention, the content ratio of the solid catalyst component, the organoaluminum compound and the external electron donating compound can be arbitrarily selected in the range where the effect of the present invention can be obtained, and is not particularly limited.
The olefin polymerization catalyst according to the present invention preferably contains 1 to 2000 moles, and more preferably 50 to 1000 moles of the organoaluminum compound per mole of titanium atom in the solid catalyst component.
In addition, the catalyst for olefins polymerization according to the present invention contains a total of 1 to 200 moles of the external electron donor compound per mole of titanium atom in the solid catalyst component contained in the catalyst for olefins polymerisation. Is preferable, containing 2 to 150 mol is more preferable, and containing 5 to 100 mol is more preferable.
Furthermore, the olefin polymerization catalyst according to the present invention preferably contains 0.001 to 10 moles of the external electron donor compound in total per mole of the organoaluminum compound contained in the olefin polymerization catalyst. It is more preferable to contain 0.002 to 2 mol, and further preferable to contain 0.002 to 0.5 mol.

Next, the method for producing the olefin polymer according to the present invention will be described.
The process for producing an olefin polymer according to the present invention is characterized by polymerizing an olefin in the presence of the olefin polymerization catalyst according to the present invention.

  Examples of the olefins to be subjected to the polymerization include one or more selected from ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene and vinylcyclohexane, etc. One or more selected from butenes is preferred, and propylene is more preferred.

When olefins are polymerized using the olefins polymerization catalyst according to the present invention, preparation of the olefins polymerization catalyst and polymerization of the olefins may be performed simultaneously, in which case each of the olefins polymerization catalyst may be formed. Although the order of contacting the components is arbitrary, it is desirable to first charge the organoaluminum compound into the polymerization system, then contact the external electron donor compound, and further contact the solid catalyst component for olefins polymerization.
The polymerization of olefins can be carried out in the presence or absence of an organic solvent, and olefin monomers such as propylene can be used in either gas or liquid state.

  As a polymerization method of olefins, a conventionally known method used for polymerization of a C2-C10 1-olefin can be used. For example, a gas or liquid monomer is supplied in the presence of an organic solvent to perform polymerization. Slurry polymerization, bulk polymerization in which polymerization is carried out in the presence of a liquid monomer such as liquefied propylene, gas phase polymerization in which polymerization is carried out in the presence of a gaseous monomer, etc. are mentioned, and any of these methods carry out the polymerization reaction Polymerization by gas phase polymerization is preferred.

  Also, for example, the method described in Japanese Patent No. 2578408, the continuous gas phase polymerization method described in Japanese Patent No. 439264, Japanese Patent Laid-Open No. 2009-292964 etc., and the polymerization method described in Japanese Patent No. 2766523 are also applied. It is possible. Each of the above polymerization methods can be carried out either batchwise or continuously. Furthermore, the polymerization reaction may be carried out in one step or in two or more steps.

  In the case of polymerizing olefins using the catalyst for olefins polymerization according to the present invention, as a polymerization reactor, for example, a reactor such as an autoclave with a stirrer, a fluid tank and the like can be mentioned. The powdery polymer can be contained in the stationary phase and motion can be imparted using a stirrer or fluid bed.

The molecular weight of the polymer to be obtained can be adjusted and set in a wide range by the addition of regulators customary in the polymerization art, for example hydrogen.
In order to remove the heat of polymerization, a liquid readily volatile hydrocarbon such as butane may be supplied and vaporized in the polymerization zone.

The polymerization temperature is preferably 200 ° C. or lower, more preferably 100 ° C. or lower, and still more preferably 50 to 90 ° C.
The polymerization pressure is preferably normal pressure to 10 MPa, more preferably normal pressure to 5 MPa, and still more preferably 1 to 4 MPa.

In the method for producing an olefin polymer according to the present invention, the obtained olefin polymer preferably has a melt flowability (melt flow rate (MFR)) of 1 kg / 10 min or more, preferably 1 to 5 kg / 10. It is more preferable that it is a minute, and further preferable that it is 2 to 4 kg / 10 min.
When the melt flowability is in the above range, a film or the like can be easily formed from the obtained polymer.

  In the present application document, the melt fluidity of the olefin polymer means a value measured by the JIS K 7210 B method.

In the method for producing an olefin polymer according to the present invention, the obtained olefin polymer preferably has a melting point (Tm) of less than 160 ° C., more preferably 157 to 160 ° C.
In the present application document, the melting point (Tm) of the olefin polymer means a value measured by the JIS K 7121 method.

In the method for producing an olefin polymer according to the present invention, the obtained olefin polymer preferably has an isotactic pentad fraction (NMR-mmmm) of 91% or more as measured by ¹³ C-NMR. And 91.5% or more is more preferable, and 91.5 to 95.0% is more preferable.

  Pentad means a unit chain consisting of 4 adjacent monomer units inserted by selecting the same prochiral surface, and isotactic pentad is a unit consisting of 4 adjacent propylene units having an isotactic structure. Means chain. Further, in the present invention, the isotactic pentad fraction refers to the percentage of the isotactic pentad number to the total pentad number of the olefin chain portion of the polymer constituting the isotactic polypropylene-based particles (A) The upper limit that can be measured is 100%.

  When the isotactic pentad fraction (NMR-mmmm) of the polymer at a melting point (Tm) of less than 160 ° C. is within the above range, it becomes possible to maintain stereoregularity, and the melt tension (Koshi) of polypropylene Can be improved, and the "sag" at the time of forming the polymer into a film is alleviated, so that the processability to a film or the like can be improved.

In addition, in this application document, the isotactic pentad fraction (mm mm) of a polymer measures ¹³ C-NMR spectrum, and A. It means a value determined according to the method described in Zambelli; Macromolecules, 6, 925 (1973), 8, 687 (1975) and 13, 267 (1980).

  According to the present invention, by homopolymerizing propylene using the catalyst for olefins polymerization according to the present invention, the melting point is as low as 160 ° C. and the steric rule without coexistence of α-olefin other than propylene such as ethylene. It is possible to provide a method for producing a propylene homopolymer (homopolypropylene) which is highly maintained and has excellent melt tension.

(Example)
EXAMPLES The present invention will next be described in more detail by way of examples, which are merely illustrative and do not limit the present invention.

Example 1
1. Preparation of solid catalyst component 10 g (87.4 millimoles) of diethoxymagnesium, 45 ml of toluene, 30 ml of titanium tetrachloride are added to a flask equipped with a stirrer and sufficiently replaced with nitrogen gas and then 500 ml of a flask. 6.6 mmol (1.8 g) of normal butyl was added, the temperature was raised to 100 ° C., and the reaction was carried out for 120 minutes while maintaining the temperature of 100 ° C. After completion of the reaction, the reaction product was washed three times with 90 ml of toluene at 100.degree.
Then, 90 ml of toluene and 2 mmol of dimethyl diisobutyl malonate (0.5 g, 0.023 mol per mol of magnesium atom contained in magnesium) are added, and the temperature is raised to 100 ° C., and the reaction is carried out for 5 minutes while maintaining 100 ° C. After the addition, the supernatant was removed.
Then, 55 ml of toluene containing 40% by volume of titanium tetrachloride (a mixed solution of 22.5 ml of titanium tetrachloride and 32.5 ml of toluene) is added, the temperature is raised to 100 ° C., and the mixture is stirred at 100 ° C. for 5 minutes. After the operation of removing the supernatant was repeated twice, the solid catalyst component-containing solution was obtained by washing six times with 55 ml of n-heptane at 40 ° C.
The solid content of the solid catalyst component-containing liquid is separated, and the titanium content in the obtained solid content (solid catalyst component), the first internal electron donor compound content, and the second internal electron donor compound are contained. The amount was measured to be 4.4% by mass, 9.6% by mass, and 2.7% by mass, respectively.

The titanium content in the solid content and the contents of the first internal electron donor and the second internal electron donor were measured as follows.
<Titanium content in solid content>
The titanium content in the solid content was measured according to the method of JIS M 8301.
<Content of internal electron donor compound in solid content>
The content of the internal electron donating compound was determined by using gas chromatography (GC-14B, manufactured by Shimadzu Corporation) under the following conditions. Moreover, about the number-of-moles of each component, it calculated | required from the measurement result of gas chromatography using the calibration curve previously measured in known concentration.
(Measurement condition)
・ Column: Packed column (φ 2.6 × 2.1 m, Silicone SE-30 10%, Chromosorb WAW DMCS 80/100, GL Science Co., Ltd.)
・ Detector: FID (Flame Ionization Detector, hydrogen flame ionization detector)
Carrier gas: Helium, flow rate 40 ml / min Measurement temperature: vaporization chamber 280 ° C, column 225 ° C, detector 280 ° C

2. Formation of a polymerization catalyst and polymerization: In a 1.5 l stirred autoclave with an internal volume completely substituted with propylene gas, heptane 700 mL, triethylaluminum 2.1 mmol, cyclohexylmethyldiethoxysilane (CMDMS) 0.0525 mmol and The solid catalyst component was charged as 0.00525 millimoles as a titanium atom to form a polymerization catalyst. Thereafter, 10 ml of hydrogen gas was introduced, prepolymerization was carried out at 20 ° C. for 30 minutes, and then the temperature was raised, and slurry polymerization was carried out at 70 ° C. for 120 minutes. At this time, the polymerization activity per 1 g of solid catalyst component, the melt flow rate (MFR) in the formed polymer, the melting point (Tm) of the polymer, and the value of the isotactic pentad (mmmm) of the polymer by the following method It was measured. The results are shown in Table 1.

<Polymerization activity per 1 g of solid catalyst component>
The polymerization activity per 1 g of the solid catalyst component was determined by the following formula.
Polymerization activity (g-pp / g-catalyst) = mass of polymer (g) / mass of solid catalyst component (g)

Melt flowability (MFR) of polymer
The melt flow rate (MFR) indicating the melt flowability of the polymer was measured according to ASTM D 1238, JIS K 7210.

<Melting point (Tm) of polymer>
The temperature at the position of the maximum peak in the endothermic curve of differential scanning calorimetry (DSC) was taken as the melting point (Tm) of the polymer. In the measurement, the sample is packed in an aluminum pan, heated to 250 ° C. at 10 ° C./min by differential scanning calorimetry (DSC) (manufactured by SII, EXSTAR 6000), and kept at 250 ° C. for 20 minutes, then 5 ° C. / The temperature was lowered to 20 ° C. in a minute and then the temperature was raised at 10 ° C./min, and the endothermic curve was measured.

Polymer isotactic pentad (mmmm)
The isotactic pentad (mm mm) of the polymer was measured by ¹³ C-NMR spectrum, and A. Macromoleculars, 6, 925 (1973), 8, 687 (1975) and 13, 267 (1980). In addition, ¹³ C-NMR measurement was performed under the following conditions using JNM-made JNM-ECA400.
< ¹³ C-NMR measurement conditions>
Measurement mode: Proton decoupling method
Pulse width: 7.25 μsec
Pulse repetition time: 7.4 sec
Accumulated number of times: 10,000 times
Solvent: Tetrachloroethane-d2
Sample concentration: 200 mg / 3.0 ml

(Example 2)
Polymerization was carried out in the same manner as in Example 1 except that 0.0525 millimole of cyclohexylmethyldiethoxysilane (CMDMS) was changed to 0.105 millimole in “2. Formation and polymerization of polymerization catalyst” in Example 1. . At this time, the polymerization activity per 1 g of the solid catalyst component, the melt flow rate (MFR) in the formed polymer, the melting point (Tm) of the polymer, and the value of isotactic pentad (mmmm) of the polymer It measured by the same method. The results are shown in Table 1.

(Example 3)
The polymerization was carried out in the same manner as in Example 1 except that 0.0525 millimole of cyclohexylmethyldiethoxysilane (CMDMS) was changed to 0.173 millimole in “2. Formation and polymerization of polymerization catalyst” of Example 1. At this time, the polymerization activity per 1 g of the solid catalyst component, the melt flow rate (MFR) in the formed polymer, the melting point (Tm) of the polymer, and the value of isotactic pentad (mmmm) of the polymer It measured by the same method. The results are shown in Table 1.

(Example 4)
The synthesis of the solid catalyst component was carried out in the same manner as in Example 1 except that 2 millimoles of diethyl diisobutyl malonate was changed to 1 millimole in “1. Synthesis of solid catalyst component” in Example 1. The solid content of the solid catalyst component was separated, and the content of titanium, the content of dinormal butyl phthalate and the content of diethyl diisobutyl malonate in the obtained solid content were measured, and each was 4.6% by mass , 10.0 mass%, and 1.2 mass%. The formation and polymerization of a polymerization catalyst were carried out in the same manner as in Example 1 using this solid catalyst component. At this time, the polymerization activity per 1 g of the solid catalyst component, the melt flow rate (MFR) in the formed polymer, the melting point (Tm) of the polymer, and the value of isotactic pentad (mmmm) of the polymer It measured by the same method. The results are shown in Table 1.

(Example 5)
The polymerization was carried out in the same manner as in Example 1 except that 0.0525 mmol of cyclohexylmethyldiethoxysilane (CMDMS) was changed to 0.105 mmol in “2. Formation and polymerization of polymerization catalyst” of Example 4. At this time, the polymerization activity per 1 g of the solid catalyst component, the melt flow rate (MFR) in the formed polymer, the melting point (Tm) of the polymer, and the value of isotactic pentad (mmmm) of the polymer It measured by the same method. The results are shown in Table 1.

(Example 6)
The polymerization was carried out in the same manner as in Example 1 except that 0.0525 millimole of cyclohexylmethyldiethoxysilane (CMDMS) was changed to 0.1575 millimole in “2. Formation and polymerization of polymerization catalyst” of Example 4. At this time, the polymerization activity per 1 g of the solid catalyst component, the melt flow rate (MFR) in the formed polymer, the melting point (Tm) of the polymer, and the value of isotactic pentad (mmmm) of the polymer It measured by the same method. The results are shown in Table 1.

(Example 7)
1. Synthesis of solid catalyst component The solid catalyst component was synthesized in the same manner as in Example 1 except that 2 mmol of dimethyl diisobutyl malonate was changed to 1 mmol of diethyl phthalate in "1. Synthesis of solid catalyst component" in Example 1. The The solid content of the obtained solid catalyst component-containing liquid is separated, and the titanium content, di-n-butyl phthalate content and the diethyl phthalate content in the obtained solid content (solid catalyst component) are measured. And 4.9% by mass, 9.0% by mass, and 1.5% by mass, respectively.
2. Formation and polymerization of polymerization catalyst In "2. Formation and polymerization of polymerization catalyst" of Example 1, the above 1. The polymerization catalyst was formed and polymerized in the same manner as in Example 1 except that 0.0525 millimoles of cyclohexylmethyldiethoxysilane (CMDMS) was changed to 0.021 millimoles using the solid catalyst component obtained in 1. above.
At this time, the polymerization activity per 1 g of the solid catalyst component, the melt flow rate (MFR) in the formed polymer, the melting point (Tm) of the polymer, and the value of isotactic pentad (mmmm) of the polymer It measured by the same method. The results are shown in Table 1.

(Example 8)
Example “Example 2. Formation and polymerization of polymerization catalyst” of Example 7 except that 0.021 millimole of cyclohexylmethyldiethoxysilane (CMDMS) was changed to 0.105 millimole and hydrogen amount was changed from 10 ml to 20 ml The polymerization was carried out as in 7.
At this time, the polymerization activity per 1 g of the solid catalyst component, the melt flow rate (MFR) in the formed polymer, the melting point (Tm) of the polymer, and the value of isotactic pentad (mmmm) of the polymer It measured by the same method. The results are shown in Table 1.

(Example 9)
The polymerization was carried out in the same manner as in Example 7 except that 0.021 millimole of cyclohexylmethyldiethoxysilane (CMDMS) was changed to 0.173 millimole in “2. Formation and polymerization of polymerization catalyst” of Example 7. At this time, the polymerization activity per 1 g of the solid catalyst component, the melt flow rate (MFR) in the formed polymer, the melting point (Tm) of the polymer, and the value of isotactic pentad (mmmm) of the polymer It measured by the same method. The results are shown in Table 1.

(Comparative example 1)
Instead of adding 90 ml of toluene and 2 mmol of dimethyl diisobutyl malonate in “1. Synthesis of solid catalyst component” in Example 1, only 90 ml of toluene was added, and diethyl diisobutyl malonate was not added. The solid catalyst component was synthesized in the same manner as Example 1. The solid content of the obtained solid catalyst component-containing liquid was separated, and the titanium content and the phthalic acid diester content in the obtained solid content (solid catalyst component) were measured. And 10.9 mass%.
Using this solid catalyst component, formation and polymerization of a polymerization catalyst were carried out in the same manner as in Example 1 except that the addition amount of cyclohexylmethyldiethoxysilane (CMDMS) was changed from 0.0525 millimole to 0.021 millimole.
At this time, the polymerization activity per 1 g of the solid catalyst component, the melt flow rate (MFR) in the formed polymer, the melting point (Tm) of the polymer, and the value of isotactic pentad (mmmm) of the polymer It measured by the same method. The results are shown in Table 1.

From Table 1, in Examples 1 to 9, since the solid catalyst component for olefin polymerization according to the present invention is used, while showing a low melting point of less than 160 ° C. under high polymerization activity, ¹³ The isotactic pentad fraction (NMR-mmmm) measured by C-NMR is as high as 91% or more, and it turns out that the polypropylene which can maintain high stereoregularity is obtained, film formation of such polypropylene When used in the above, the melt tension (stiffness) becomes high, and it is understood that the "sag" at the time of film formation is improved, and the amount of stickiness component can also be suppressed.

On the other hand, according to Table 1, in Comparative Example 1, the solid catalyst component for olefins polymerization is not a specific one containing a predetermined amount of the second internal electron donor compound together with the first internal electron donor compound, Since the formation of non-stereospecific active sites in the solid catalyst component is not suppressed, and reaction byproducts and excess titanium component remain in the solid catalyst component, the melting point is less than 160 ° C. In the above, since the isotactic pentad fraction (NMR-mmmm) measured by ¹³ C-NMR is reduced to less than 91%, the melt tension (Kosi) when used for film production is low, In addition, it can be seen that the amount of tackiness component at the time of molding is increased.

  According to the present invention, a propylene homopolymer (homopolypropylene) having a low melting point of less than 160 ° C. and a high degree of stereoregularity and excellent melt tension even without coexistence of an α-olefin other than propylene such as ethylene It is possible to provide a solid catalyst component for olefins polymerization which can be produced under high polymerization activity, a method for producing a solid catalyst component for olefins polymerization, a catalyst for olefins polymerization and a method for producing olefin polymers.

Claims (14)

A first step of contacting and reacting a magnesium compound, a titanium halogen compound, and a first internal electron donor compound, and then washing
After contacting and reacting a 0.001 to 0.1 mole of a second internal electron donor compound per mole of magnesium atom contained in the magnesium compound with the obtained product in the presence of a hydrocarbon solvent A second step of removing the hydrocarbon solvent,
A third step of washing one or more times with an organic solvent containing more than 5% by volume and 50% by volume or less of a titanium halogen compound and a fourth step of washing one or more times with an organic solvent not containing a titanium halogen compound Solid catalyst component for olefins polymerization characterized by being.   The first internal electron donor compound or the second internal electron donor compound is selected from phthalic acid diester, malonic acid diester, maleic acid diester, succinic acid diester, alkoxyalkyl ester, cyclohexene dicarboxylic acid diester and cyclohexane dicarboxylic acid diester The solid catalyst component for olefin polymerization according to claim 1, which is one or more selected.   The first internal electron donor compound is one or more selected from phthalic acid diester, cyclohexene dicarboxylic acid diester and cyclohexanedicarboxylic acid diester, and the second internal electron donor compound is phthalic acid diester, malonic acid diester, The solid catalyst component for olefin polymerization according to claim 1, which is one or more selected from maleic acid diesters, succinic acid diesters, alkoxyalkyl esters, cyclohexene dicarboxylic acid diesters and cyclohexane dicarboxylic acid diesters.   The first internal electron donor compound is one or more selected from di-n-butyl phthalate and diisobutyl phthalate, and the second internal electron donor compound is di-n-butyl phthalate and phthalic acid The solid catalyst component for olefins polymerization according to claim 1, which is at least one selected from phthalic acid diesters other than diisobutyl and malonic acid diesters. A first step of bringing a magnesium compound, a titanium halogen compound and a first internal electron donor compound into contact with each other, reacting them, and then washing them;
After contacting and reacting a 0.001 to 0.1 mole of a second internal electron donor compound per mole of magnesium atom contained in the magnesium compound with the obtained product in the presence of a hydrocarbon solvent A second step of removing the hydrocarbon solvent,
A third step of washing one or more times with an organic solvent containing more than 5% by volume and 50% by volume or less of a titanium halogen compound and a fourth step of washing one or more times with an organic solvent not containing a titanium halogen compound The manufacturing method of the solid catalyst component for olefins polymerization characterized by these.   The first internal electron donating compound or the second internal electron donating compound may be phthalic acid diester, malonic acid diester, maleic acid diester, succinic acid diester, alkoxyalkyl ester, cyclohexene dicarboxylic acid diester and cyclohexane dicarboxylic acid diester The method for producing a solid catalyst component for olefins polymerization according to claim 5, which is one or more selected from   The first internal electron donor compound is one or more selected from phthalic acid diester, cyclohexene dicarboxylic acid diester and cyclohexanedicarboxylic acid diester, and the second internal electron donor compound is phthalic acid diester, malonic acid diester, The method for producing a solid catalyst component for olefins polymerization according to claim 5, which is one or more selected from maleic acid diesters, succinic acid diesters, alkoxyalkyl esters, cyclohexene dicarboxylic acid diesters and cyclohexane dicarboxylic acid diesters.   The first internal electron donor compound is one or more selected from dibutyl phthalate and diisobutyl phthalate, and the second internal electron donor compound is di-phthalic acid. The method for producing a solid catalyst component for olefins polymerization according to claim 5, which is one or more selected from phthalic acid diesters other than n-butyl and phthalic acid diisobutyl and malonic acid diesters. (I) The solid catalyst component for olefins polymerization according to any one of claims 1 to 4, and (II) the following general formula (1):
R ¹ _p AlQ _3-p (1)
(In the formula, R ¹ is an alkyl group having 1 to 6 carbon atoms, Q is a hydrogen atom or a halogen atom, p is 0 <a real number of p ≦ 3, each of R ¹ when R ¹ existing in plural numbers Olefins characterized in that they may be the same or different, and when there are a plurality of Q, each Q may be the same or different) and is brought into contact with an organoaluminum compound Polymerization catalyst.   The catalyst for olefins polymerization according to claim 9, which is further brought into contact with (III) an external electron donating compound. The (III) external electron donating compound is represented by the following general formula (2):
R ² _q Si (OR ³ ) _4-q (2)
(Wherein R ² represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a phenyl group, a vinyl group, an allyl group, an aralkyl group, an alkylamino group having 1 to 12 carbon atoms, or carbon When it is a dialkylamino group of the number 1 to 12, and a plurality of R ² are present, each R ² may be the same or different.R ³ is an alkyl group having 1 to 4 carbon atoms, 3 carbon atoms 6 cycloalkyl group, a phenyl group, a vinyl group, an allyl group or an aralkyl group, if R ³ there are a plurality each R ³ may be different even in the same .q is 0 ≦ q ≦ It is an integer of 3.)
11. The catalyst for olefins polymerization according to claim 10, which is one or more organosilicon compounds selected from   A process for producing an olefin polymer comprising polymerizing olefins in the presence of the catalyst for olefins polymerization according to any one of claims 9 to 11.   The method for producing an olefin polymer according to claim 12, wherein the olefin is propylene. The olefin polymer obtained has an isotactic pentad fraction of 91.0% or more at a melt flow rate of 1.0 kg / 10 minutes or more and a melting point of 157 to 160 ° C. The manufacturing method of the olefins polymer as described in-.