阅读说明：本技术 聚乙烯组合物 (Polyethylene composition ) 是由 四方和也 于 2018-07-24 设计创作，主要内容包括：本发明涉及具有下述特征(A)和(B)的聚乙烯组合物。(A)在通过利用交叉分级色谱(CFC)的升温洗脱分级(TREF)测定每1℃的洗脱量而得到的洗脱温度-累积洗脱量曲线中,从50℃到98℃的累积洗脱比例为50质量％以上且小于80质量％。(B)在利用交叉分级色谱(CFC)的升温洗脱分级(TREF)以每1℃回收的洗脱成分中,在85℃以上且小于105℃的温度下,具有至少一种重均分子量(M<Sub>w</Sub>)为20万以上的洗脱成分。(The invention relates to a polyethylene composition having the following characteristics (A) and (B). (A) In an elution temperature-cumulative elution amount curve obtained by measuring an elution amount per 1 ℃ by Temperature Rising Elution Fractionation (TREF) of a cross-fractionation chromatography (CFC), the cumulative elution ratio from 50 ℃ to 98 ℃ is 50% by mass or more and less than 80% by mass. (B) At least one weight average molecular weight (M) in an eluted component recovered per 1 ℃ by Temperature Rising Elution Fractionation (TREF) of cross-fractionation chromatography (CFC) at a temperature of 85 ℃ or more and less than 105 ℃ w ) The elution components were 20 ten thousand or more.)

1. A polyethylene composition, wherein the polyethylene composition has the following features (a) and (B):

(A) in an elution temperature-cumulative elution amount curve obtained by measuring an elution amount per 1 ℃ by Temperature Rising Elution Fractionation (TREF) of cross-fractionation chromatography (CFC), the cumulative elution ratio from 50 ℃ to 98 ℃ is 50% by mass or more and less than 80% by mass; and

(B) at least one weight average molecular weight (M) in an eluted component recovered per 1 ℃ by Temperature Rising Elution Fractionation (TREF) of cross-fractionation chromatography (CFC) at a temperature of 85 ℃ or more and less than 105 ℃_w) The elution components were 20 ten thousand or more.

2. The polyethylene composition of claim 1, wherein,

when the sieving was performed based on JIS Z8815 using a sieve having a sieve opening size of 300 μm, there were no components remaining on the sieve.

3. The polyethylene composition according to claim 1 or 2, wherein,

the polyethylene composition has a chlorine content of 50 mass ppm or less.

4. A polyethylene composition according to any of claims 1 to 3 wherein,

the polyethylene composition has a content of an additive for the purpose of imparting flowability of 5000 mass ppm or less.

5. The polyethylene composition according to any of claims 1 to 4, wherein,

in an elution temperature-cumulative elution amount curve obtained by measuring the elution amount per 1 ℃ by Temperature Rising Elution Fractionation (TREF) using cross-fractionation chromatography (CFC), the cumulative elution ratio from 50 ℃ to 94 ℃ is less than 40% by mass.

6. The polyethylene composition according to any one of claims 1 to 5, wherein,

in an elution temperature-cumulative elution amount curve obtained by measuring the elution amount per 1 ℃ by Temperature Rising Elution Fractionation (TREF) of a cross-fractionation chromatography (CFC), the cumulative elution ratio from 50 ℃ to 94 ℃ is 10% by mass or more.

7. The polyethylene composition according to any one of claims 1 to 6, wherein,

the elution temperature-elution amount curve obtained by measuring the elution amount per 1 ℃ by Temperature Rising Elution Fractionation (TREF) of cross-fractionation chromatography (CFC) has 3 or more peaks.

8. The polyethylene composition according to any one of claims 1 to 7, wherein,

the polyethylene composition comprises a polyethylene powder and, optionally,

when the polyethylene powder was sieved using a sieve having sieve opening sizes of 53 μm, 75 μm, 106 μm, 150 μm, 212 μm and 300 μm based on JIS Z8815 and classified into various categories,

weight average molecular weight M of the coarsest particle side class₁Weight average molecular weight M of the largest proportion class₂And the weight average molecular weight M of the type on the side of the finest powder₃Satisfies the following relation of formula 1:

0.8≤M₁/M₂m is not less than 1.2 and not more than 0.8₃/M₂Less than or equal to 1.2, formula 1.

9. The polyethylene composition according to any one of claims 1 to 8, wherein,

24g of a liquid paraffin having an average molecular weight of 450 or more and less than 550 was kneaded at a set temperature of 114 ℃ for 10 minutes at a rotation speed of 5rpm using a small mixing extruder (a product of Toyo Seiki Seisaku-Sho Ltd. "Main model No. 40C 150", a mixer model No.: R-60), 16g of the polyethylene composition and 0.4g of tetrakis [ methylene (3, 5-di-t-butyl-4-hydroxyhydrocinnamate) ] methane were added, the rotation speed was set to 30rpm and the mixture was kneaded for 3 minutes under a condition that the set temperature was increased from 114 ℃ to 163 ℃ for 6 minutes, and in a torque curve obtained at this time, the difference between the resin temperature at the time when the peak having the largest torque was detected and the resin temperature at the time when the peak having the second largest torque was detected was 25 ℃ or less.

Technical Field

The present invention relates to polyethylene compositions.

Background

Polyethylene is used for various applications such as sheets, films, and molded articles, and a raw material for a separator of a battery is also one of important applications. The separator is a porous film used for the main purpose of separating a positive electrode and a negative electrode in a battery and allowing only ions to pass therethrough. Other purposes include a strength for securing the strength of the battery, a shutdown (hereinafter, also referred to as "fusing") function for preventing the risk of runaway of the battery reaction when the temperature inside the battery is increased, and the like. Further, it is required to improve these characteristics at the same time.

Polyethylene, which is a raw material of a separator, is generally produced in a powdery form as polyethylene having a higher molecular weight and a higher density than general-purpose polyethylene used for sheets, films, molded bodies, and the like. The reason why polyethylene as a raw material of the separator has a high molecular weight and a high density is to ensure the strength of the separator. The reason why the polyethylene as a raw material of the separator is in a powdery form is that the processability is poor due to a high molecular weight, so that granulation is difficult, and the powdery form is more excellent in processability.

In order to obtain an excellent separator, many studies and developments have been made. One of the problems is to control thermal shrinkage during film formation. Generally, a process of producing a microporous film or the like includes a step of stretching. In general, after the stretching step, an annealing step for relaxing molecular orientation (hereinafter, also referred to as "heat setting") is performed to suppress thermal shrinkage after stretching and thermal shrinkage in a use environment. In the heat setting step, molecular motion is performed by a component that easily performs molecular motion even at a low temperature (hereinafter, also referred to as an "amorphous component"), and the molecular orientation is relaxed. However, high density polyethylene having high crystallinity has a problem that the relaxation of molecular orientation is insufficient due to a small proportion of amorphous components, and the thickness of the microporous film is unstable due to heat shrinkage or the like.

As a method for solving this problem, the following methods are known: by appropriately adjusting the average molecular weight and the molecular weight distribution of polyethylene, it is possible to ensure appropriate molecular mobility in a low-temperature state and to efficiently perform an annealing step (for example, see patent document 1).

Further, a trade-off relationship that the processability is deteriorated when the average molecular weight of polyethylene is increased in order to increase the strength of the separator is also listed as one of the main problems. In order to solve this problem, the following methods are known: by appropriately adjusting the average molecular weight and the molecular weight distribution of polyethylene, excellent mechanical strength is imparted to a molded body, and excellent solubility or meltability is ensured (for example, see patent document 2). In order to solve the same problem, the following methods are also known: the processing conditions (amount of solvent used, kneading temperature, kneading torque, etc.) of the polyethylene powder are controlled (for example, see patent document 3).

Disclosure of Invention

Problems to be solved by the invention

The inventions of patent documents 1 to 3 are inventions focusing on the viewpoint of securing the strength of the film or controlling the thermal shrinkage, but no study has been made to further achieve the fusing function. Further, the inventions of patent documents 1 to 3 use polyethylene having high crystallinity, and therefore the fusing function at low temperatures is insufficient. The inventions of patent documents 1 to 3 also have the following problems: since polyethylene has a high molecular weight, it has extremely poor flowability, and takes a long time from the start to the end of melting.

Accordingly, an object of the present invention is to provide a polyethylene composition which can impart excellent strength, excellent fusing ability, and excellent slit processability when processed into a separator.

Means for solving the problems

The present inventors have made intensive studies to solve the above problems, and as a result, have found that when a polyethylene composition is kneaded while heating the composition together with a solvent, the resin temperature of the maximum torque peak observed and the resin temperature of the second largest peak are observedWhen the difference between the resin temperatures is equal to or less than a predetermined temperature difference, that is, when the swelling and melting process of the polyethylene during kneading is completed at or less than the predetermined temperature difference, and when the amount of the eluting component at 98 ℃ is within a specific range in an elution temperature-cumulative elution amount curve obtained by Temperature Rising Elution Fractionation (TREF) of the cross-fractionation chromatography (CFC), and when the amount of the eluting component is within a specific temperature range in an elution temperature-elution amount curve obtained by Temperature Rising Elution Fractionation (TREF) of the cross-fractionation chromatography (CFC), at least one weight average molecular weight (M) is present within a specific temperature range_w) The present inventors have completed the present invention by solving the above-mentioned problems when the amount of the eluting component is 20 ten thousand or more.

That is, the present invention relates to the following.

[1]

A polyethylene composition, wherein the polyethylene composition has the following features (a) and (B):

(A) in an elution temperature-cumulative elution amount curve obtained by measuring an elution amount per 1 ℃ by Temperature Rising Elution Fractionation (TREF) of a cross-fractionation chromatography (CFC), the cumulative elution ratio from 50 ℃ to 98 ℃ is 50% by mass or more and less than 80% by mass.

(B) At least one weight average molecular weight (M) in an eluted component recovered per 1 ℃ by Temperature Rising Elution Fractionation (TREF) of cross-fractionation chromatography (CFC) at a temperature of 85 ℃ or more and less than 105 ℃_w) The elution components were 20 ten thousand or more.

[2]

The polyethylene composition of [1], wherein, when the sieving is performed using a sieve having a mesh size of 300 μm based on JIS Z8815, there is no component remaining on the sieve.

[3]

The polyethylene composition according to [1] or [2], wherein the chlorine content of the polyethylene composition is 50 mass ppm or less.

[4]

The polyethylene composition according to any one of [1] to [3], wherein a content of the additive for the purpose of imparting flowability of the polyethylene composition is 5000 mass ppm or less.

[5]

The polyethylene composition as described in any one of [1] to [4], wherein, in an elution temperature-cumulative elution amount curve obtained by measuring an elution amount per 1 ℃ by Temperature Rising Elution Fractionation (TREF) by Cross Fractionation Chromatography (CFC), a cumulative elution ratio from 50 ℃ to 94 ℃ is less than 40 mass%.

[6]

The polyethylene composition according to any one of [1] to [5], wherein, in an elution temperature-cumulative elution amount curve obtained by measuring an elution amount per 1 ℃ by Temperature Rising Elution Fractionation (TREF) of a cross-fractionation chromatography (CFC), a cumulative elution ratio from 50 ℃ to 94 ℃ is 10% by mass or more.

[7]

The polyethylene composition according to any one of [1] to [6], wherein the polyethylene composition has 3 or more peaks in an elution temperature-elution amount curve obtained by measuring an elution amount per 1 ℃ by Temperature Rising Elution Fractionation (TREF) of a cross-fractionation chromatography (CFC).

[8]

The polyethylene composition according to any one of [1] to [7], wherein,

the polyethylene composition comprises a polyethylene powder and, optionally,

when the above polyethylene powder was sieved based on JIS Z8815 using a sieve having mesh sizes of 53 μm, 75 μm, 106 μm, 150 μm, 212 μm and 300 μm and classified into each class,

weight average molecular weight M of the coarsest particle side class₁Weight average molecular weight M of the largest proportion class₂And the weight average molecular weight M of the type on the side of the finest powder₃Satisfies the following relation of formula 1.

0.8≤M₁/M₂M is not less than 1.2 and not more than 0.8₃/M₂Less than or equal to 1.2 formula 1

[9]

The polyethylene composition according to any one of [1] to [8], wherein 24g of liquid paraffin having an average molecular weight of 450 or more and less than 550 is kneaded at a set temperature of 114 ℃ and a rotation speed of 5rpm for 10 minutes using a small mixing extruder ("Main model 40C 150" manufactured by Toyo Seiki Seisaku-Sho K.K.; mixer model: R-60), then, 16g of the above polyethylene composition and 0.4g of tetrakis [ methylene (3, 5-di-t-butyl-4-hydroxyhydrocinnamate) ] methane were added thereto, the mixture was kneaded at 30rpm for 3 minutes, then kneading was carried out under the condition that the set temperature was raised from 114 ℃ to 163 ℃ over 6 minutes, in the torque curve obtained at this time, the difference between the resin temperature at the time when the peak of the maximum torque is detected and the resin temperature at the time when the second maximum torque is detected is 25 ℃ or less.

Effects of the invention

According to the present invention, a polyethylene composition which can impart excellent strength and fusing property and has good slit processability when processed into a separator can be provided.

Drawings

FIG. 1 shows the elution temperature-cumulative elution amount curve obtained by the measurement of cross-fractionation chromatography (CFC).

FIG. 2 shows the elution temperature-elution volume curve obtained by cross-fractionation chromatography (CFC) measurement.

Detailed Description

Hereinafter, a mode for carrying out the present invention (hereinafter, referred to as "the present embodiment") will be described in detail. The present invention is not limited to the following embodiments, and various modifications can be made within the scope of the present invention.

In the present specification, the "fusing property" refers to a property that enables fusing even at low temperature and has a sufficiently high fusing speed, for example, when processed into a separator.

[ polyethylene composition ]

The polyethylene composition of the present embodiment has the following features (a) and (B). The polyethylene composition of the present embodiment can impart excellent strength and fusing property when processed into a separator by having the following features (a) and (B). In addition, in slit processing for adjusting the width of a film, generation of undulation, burrs, and the like in the cross section of the film can be sufficiently suppressed, and therefore, slit processing is excellent.

(A) In an elution temperature-cumulative elution amount curve obtained by measuring an elution amount per 1 ℃ by Temperature Rising Elution Fractionation (TREF) of a cross-fractionation chromatography (CFC), the cumulative elution ratio from 50 ℃ to 98 ℃ is 50% by mass or more and less than 80% by mass.

(B) At least one weight average molecular weight (M) in an eluted component recovered per 1 ℃ by Temperature Rising Elution Fractionation (TREF) of cross-fractionation chromatography (CFC) at a temperature of 85 ℃ or more and less than 105 ℃_w) The elution components were 20 ten thousand or more.

The polyethylene composition of the present embodiment is, for example, in the form of powder. In the following description, when the powder form is referred to, it may be referred to as "polyethylene powder".

The polyethylene composition of the present embodiment includes an ethylene-based polymer (hereinafter, also referred to as "polyethylene") as the ethylene-based polymer, there may be mentioned an ethylene homopolymer and/or a copolymer of ethylene and another comonomer copolymerizable with ethylene (for example, a binary or ternary copolymer), the bonding form of the copolymer may be random or block, the other comonomer is not particularly limited, and there may be mentioned, for example, α -olefin, an ethylene-based compound and the like, the other comonomer may be used singly or in combination of two or more, α -olefin is not particularly limited, there may be mentioned, for example, α -olefin having 3 to 20 carbon atoms, specifically, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene and the like, among these, from the viewpoint of further improving the heat resistance and strength of films and fibers and the like, the other comonomer is preferably propylene and/or 1-butene, as well as a conjugated diene, there may be mentioned, as a conjugated diene, and there may be mentioned, as a non-conjugated diene, and there may be mentioned, a conjugated diene, and the like.

The polyethylene composition of the present embodiment may be used in the form of a mixture obtained by mixing (blending) with ethylene polymers having different viscosity average molecular weights, molecular weight distributions, and the like, or may be used in the form of a mixture obtained by mixing (blending) with other resins such as low density polyethylene, linear low density polyethylene, polypropylene, polystyrene, and the like.

The polyethylene composition of the present embodiment has a cumulative elution ratio from 50 ℃ to 98 ℃ of 50% by mass or more and less than 80% by mass, preferably 52% by mass or more and less than 78% by mass, more preferably 54% by mass or more and less than 76% by mass, and particularly preferably 56% by mass or more and less than 74% by mass, in the CFC elution temperature-cumulative elution amount curve. The cumulative elution ratio is within the above range, that is, the ratio of the low molecular weight component and the high molecular weight component of the polyethylene composition of the present embodiment is within a range necessary for satisfying both the strength and the fusing ability of the separator.

The elution temperature-cumulative elution amount curve of CFC can be determined by the following method.

The column of the CFC measuring apparatus containing the filler was heated to 140 ℃ and introduced into 20ml of a sample solution (sample concentration: 1.0g/ml) prepared by dissolving polyethylene in o-dichlorobenzene, and the mixture was held for 120 minutes. Then, the column temperature was decreased to 40 ℃ at a rate of 0.5 ℃/min and then maintained for 20 minutes. Thereafter, the column temperature was adjusted as follows. First, the temperature was raised to 50 ℃ and held at 50 ℃ and then raised to 60 ℃ and held at 60 ℃. Further, the temperature was raised and maintained at 5 ℃ intervals from 60 ℃ to 75 ℃, at 3 ℃ intervals from 75 ℃ to 90 ℃, and at 1 ℃ intervals from 90 ℃ to 120 ℃. In each temperature raising step, the temperature was raised at a rate of 20 ℃/min and held at each holding temperature for 21 minutes. The concentration (% by mass) of the sample (polyethylene) eluted at the time of being held at each holding temperature for 21 minutes was measured, and an elution temperature-elution amount curve and an elution temperature-cumulative elution amount curve were obtained from the holding temperature and the concentration of the eluted sample.

In addition, the polyethylene composition of the present embodiment has a cumulative elution ratio from 50 ℃ to 94 ℃ in the elution temperature-cumulative elution amount curve of preferably less than 40% by weight, more preferably less than 38% by weight, and still more preferably less than 34% by weight. When the cumulative elution ratio up to 94 ℃ is within the above range, the amount of the low-molecular-weight component is relatively appropriate, and the fusing performance tends to be improved without lowering the strength, which is preferable.

In addition, in the elution temperature-cumulative elution amount curve, the cumulative elution ratio from 50 ℃ to 94 ℃ of the polyethylene composition of the present embodiment is preferably 10% by weight or more, more preferably 12% by weight or more, and still more preferably 14% by weight or more. When the cumulative elution ratio up to 94 ℃ is within the above range, the amount of the low-molecular-weight component is relatively appropriate, and the fusing performance tends to be improved without lowering the strength, which is preferable.

As a method of adjusting the cumulative elution ratio within the above range, for example, the following methods can be cited: the average molecular weight when polymerizing into polyethylene, for example, the amount of chain transfer agent, or the polyethylene is formed in the form of a mixture of polyethylene having a higher molecular weight and polyethylene having a lower molecular weight, and the molecular weight and the ratio thereof are adjusted. The latter method is preferably used in order to improve the fusing property, slit processability, and productivity of the separator (fine adjustment of the molecular weight of the polyethylene raw material) without lowering the strength of the film. However, it is generally difficult to uniformly mix polyethylenes having a large difference in molecular weight, and when they cannot be uniformly mixed, there arises a problem that defects increase and the film properties fluctuate. As a method for solving this problem, a method of intentionally adding a small amount of a low-molecular weight component when polymerizing polyethylene is mentioned. By polymerizing both components simultaneously, the high molecular weight component and the low molecular weight component are uniformly dispersed at the time of production, and thus the problem of mixing is solved. Further, a method of producing polyethylene having a relatively high molecular weight and polyethylene having a low molecular weight by adding a small amount of a low molecular weight component intentionally and forming them into a mixture is also effective. Examples of the method of intentionally adding a small amount of a low-molecular weight component include: feeding the catalyst to the polymerizer from three locations, one of which is adjacent to the feed location of ethylene; two catalyst feeding positions far away from the ethylene feeding position are arranged near the liquid level of the polymerizer, and a catalyst feeding position close to the ethylene feeding position is arranged near the bottom surface of the polymerizer; no baffle is arranged in the polymerizer; making the angle of the stirring blade of the polymerizer vertical; the deactivation of the catalyst is intentionally delayed in the flash tank, during which conditions of high temperature and low pressure are maintained, etc.

[ Peak of elution temperature-elution amount Curve ]

The polyethylene composition of the present embodiment has 3 or more peaks in the elution temperature-elution amount curve. In general, polyethylene has 1 to 2 peaks in the elution temperature-elution amount curve, and in the case of having 3 or more peaks, the fusing function is further excellent, and thus is preferable. A polyethylene having a small molecular weight is necessary to exhibit the fusing function, and a polyethylene having a high molecular weight is necessary to sufficiently secure the strength, and it is considered that in the case of a polyethylene having 3 or more peaks, components having a wide range of molecular weights are simultaneously contained, and therefore these properties can be simultaneously achieved. As a method for having 3 or more peaks, there can be cited a method of forming a mixture of polyethylene having a higher polyethylene molecular weight and polyethylene having a lower molecular weight, and adjusting these molecular weights and proportions.

[ weight average molecular weight ]

The polyethylene composition of the present embodiment has at least one weight average molecular weight (M) at a temperature of 85 ℃ or more and less than 105 ℃ in an elution component recovered per 1 ℃ by Temperature Rising Elution Fractionation (TREF) of a cross-fractionation chromatography (CFC)_w)20 ten thousand or more, preferably 22 ten thousand or more, and more preferably 25 ten thousand or more. Such a component having a high molecular weight tends to sufficiently secure the strength of the separator, and is therefore preferable. M of polyethylene_wFor example, it can be adjusted by allowing hydrogen to be present in the polymerization system or by changing the polymerization temperature.

[ chlorine content ]

The chlorine content (hereinafter, also referred to as "total chlorine amount") contained in the polyethylene composition of the present embodiment is preferably 50 mass ppm or less, more preferably 20 mass ppm or less, and still more preferably 5 mass ppm or less. When the total chlorine amount is 50 mass ppm or less, a polyethylene composition having more excellent thermal stability is obtained, and when a separator is produced, the long-term stability of the composition is more excellent. Further, a total chlorine amount of 5 mass ppm or less is preferable because the chlorine-containing component reacts with the antioxidant and the heat stabilizer added during processing to form a quinone compound, and yellowing of the battery separator can be sufficiently suppressed. The total chlorine content in the polyethylene composition of the present embodiment may be controlled by the production rate of polyethylene per unit catalyst. The productivity of polyethylene can be controlled by the polymerization temperature, polymerization pressure, and slurry concentration of the reactor during production. In other words, in order to increase the productivity of the polyethylene used in the present embodiment, the polymerization temperature, the polymerization pressure, the slurry concentration, or a combination thereof may be increased. In addition, as another method, the chlorine content may be further reduced by using an inert gas containing water or the like in the deactivation step after the polymerization.

[ amount of additive ]

The content of the additive for the purpose of imparting flowability (hereinafter, may be simply referred to as "additive") in the polyethylene composition of the present embodiment is preferably 5000 mass ppm or less, more preferably 4000 mass ppm or less, and still more preferably 3000 mass ppm or less. Additives for the purpose of imparting fluidity are also referred to as lubricants, and the substances are not particularly limited, and specific examples thereof include calcium stearate, magnesium stearate, zinc stearate, and the like. By adding a lubricant, the fluidity of the polyethylene composition is improved, the productivity is improved, or the polyethylene composition is suitable for processing applications such as stretchability. However, in the application of the separator, since the lubricant oozed out to the film surface during film formation causes problems such as adhesion to a roller and retention, it can be suitably produced by setting to 5000ppm or less. Therefore, from the viewpoint of further sufficiently suppressing bleeding while maintaining productivity and processing applicability, the content of the additive is preferably 50 mass ppm or more and 5000 mass ppm or less, more preferably 100 mass ppm or more and 4000 mass ppm or less, and further preferably 150 mass ppm or more and 3000 mass ppm or less.

[ screening ]

The polyethylene composition of the present embodiment preferably contains a polyethylene powder in a powdery form.

When the polyethylene composition of the present embodiment is subjected to sieving based on JIS Z8815 using a sieve having a mesh opening size of 300 μm, the proportion of components remaining on the sieve (components remaining on the sieve) is preferably 0.5% by mass or less, more preferably 0.2% by mass or less, and still more preferably 0.0% by mass, that is, none is present, relative to the entire polyethylene composition. When the percentage of the component remaining on the sieve is 0.5% by mass or less, the occurrence of defects (flaws) on the film surface when the separator is produced tends to be further sufficiently suppressed. When the polyethylene composition of the present embodiment contains a polyethylene powder, the polyethylene powder is classified into each of the categories by sieving the polyethylene powder based on JIS Z8815 using a sieve having mesh sizes of 53 μ M, 75 μ M, 106 μ M, 150 μ M, 212 μ M and 300 μ M, and the weight average molecular weight M of the category on the coarsest powder side₁Weight average molecular weight M of the largest proportion class₂And the weight average molecular weight M of the type on the side of the finest powder₃The relationship of the following formula 1 is preferably satisfied. The polyethylene composition of the present embodiment may contain two or more kinds of polyethylene powders having different weight average molecular weights, and in this case, each of the polyethylene powders preferably satisfies the following formula 1. In formula 1, further, M₁/M₂More preferably 0.85 to 1.15, still more preferably 0.9 to 1.1, M₃/M₂More preferably 0.85 to 1.15, and still more preferably 0.9 to 1.1.

0.8≤M₁/M₂M is not less than 1.2 and not more than 0.8₃/M₂Less than or equal to 1.2 formula 1

Satisfying the above formula 1 indicates that the molecular weight of the polyethylene powder has little variation with particle size. Whether the fine powder side has a high molecular weight or the coarse powder side has a high molecular weight during polymerization varies depending on the kind of the catalyst. In addition, the possibility of fouling or the effects of unexpected polymerization is also taken into account. For example, the coarse powder may be peeled off and pulverized in the reactor, and as a result, may be mixed therein. On the other hand, the fine powder tends to rise in the reactor, and as a result, there is a possibility that the polyethylene is polymerized at a different residence time from that of the usual polyethylene. Thus, the fine powder and the coarse powder may have molecular weights different from those of typical polyethylene, and this may cause dissolution residue of the powder or poor kneading and dispersion during processing. As a method for uniformly controlling the polymerization average molecular weight of the fine powder and the coarse powder, there can be mentioned: the selection of the polymerization catalyst, the removal of fouling by washing the inside of the polymerization vessel and piping, the inhibition of agitation in the polymerization vessel, and the like. Further, a method of removing coarse powder and fine powder from the obtained polyethylene powder is also effective.

The weight average molecular weight of the type mentioned herein is the weight average molecular weight M measured by GPC_wFor polyethylene in a high molecular weight region which cannot be measured by GPC, a viscosity average molecular weight measured by a viscometer is used. Wherein M is for the same polyethylene₁、M₂And M₃The measurement was performed by the same measurement method. In any method, the sample can be measured in a small amount, but if the amount of the sample on the sieve on the coarsest powder side is insufficient, the measurement is performed using a sample on the first stage closer to the fine powder side than the coarse powder side. The same applies to the fine powder side.

[ Torque ]

In the polyethylene composition of the present embodiment, 24g of liquid paraffin having an average molecular weight of 450 or more and less than 550 was kneaded at a set temperature of 114 ℃ and a rotation speed of 5rpm for 10 minutes using a small mixing extruder (labo plastomill) (product of toyo seiki co., ltd. "body model 40C 150", mixer model: R-60), then 16g of the polyethylene composition and 0.4g of tetrakis [ methylene (3, 5-di-t-butyl-4-hydroxyhydrocinnamate) ] methane were added, the rotation speed was set to 30rpm and the mixture was kneaded for 3 minutes, the set temperature was increased from 114 ℃ to 163 ℃ for 6 minutes, and in a torque curve obtained at this time, the difference between the resin temperature at which the maximum torque peak was detected and the resin temperature at which the second maximum torque peak was detected was, for example, 25 ℃ or less (for example, 10 ℃ or higher and 25 ℃ or lower), preferably 23 ℃ or lower, and more preferably 21 ℃ or lower. In this test, the torque forms the peak with the highest torque when the polyethylene composition swells in the solvent and the peak with the second highest torque when the resin melts, and therefore, the small temperature difference is preferable because the polyethylene is easily soluble polyethylene which rapidly transits from swelling to melting, and is more uniformly kneaded in the extruder. As a method for reducing the temperature difference, for example, a method of reducing the average molecular weight of polyethylene, a method of reducing the crystallinity of polyethylene, a method of reducing the bulk density of polyethylene, and the like are cited, but these methods are not preferable because the average molecular weight and the crystallinity tend to reduce the strength of the separator. As a method for reducing the temperature difference of the torque peak, a method of reducing the bulk density is effective in the case where the polyethylene composition is in a powder form, and specifically, a method of controlling the bulk density by dissolving and removing the carrier of the polymerization catalyst after the polymerization of polyethylene is preferable.

[ catalyst Components ]

The catalyst component used for producing the ethylene polymer constituting the polyethylene powder of the present embodiment is not particularly limited, and the ethylene polymer of the present embodiment can be produced using a ziegler-natta catalyst, a metallocene catalyst, or the like.

First, the Ziegler-Natta catalyst will be explained. The ziegler-natta catalyst is a catalyst comprising a solid catalyst component [ a ] and an organometallic compound component [ B ], the solid catalyst component [ a ] being soluble in an inert hydrocarbon solvent, and is preferably a catalyst for olefin polymerization produced by reacting an organomagnesium compound (a-1) represented by the following formula 2 with a titanium compound (a-2) represented by the following formula 3.

(A-1)：(M¹)_α(Mg)_β(R²)_a(R³)_bY¹ _c… formula 2

(in the formula, M¹Is a metal atom belonging to any one of groups 12, 13 and 14 of the periodic Table of the elements, R²And R³Is a hydrocarbon group of 2 to 20 carbon atoms, Y¹Is alkoxy, siloxy, allyloxy, amino, amido, -N ═ C-R⁴、R⁵、-SR⁶(in these formulae, R⁴、R⁵And R⁶Each independently represents a hydrocarbon group having 1 to 20 carbon atoms) and β -keto acid residue, and Y represents¹In the case of plural, they may be different from each other, α, β, a, b and c are real numbers satisfying the following relationship 0. ltoreq. α, 0 < β, 0. ltoreq.a, 0. ltoreq.b, 0. ltoreq.c, 0 < a + b, 0. ltoreq.b/(α + β). ltoreq.2, n α +2 β. ltoreq.a + b + c (where n represents M¹The valence of (3). ))

(A-2)：Ti(OR⁷)_dX¹ _(4-d)Formula 3

(wherein d is a real number of 0 to 4, R⁷Is a hydrocarbon group of 1 to 20 carbon atoms, X¹Is a halogen atom. )

The inert hydrocarbon solvent used in the reaction of (A-1) and (A-2) is not particularly limited, and specifically, there may be mentioned: aliphatic hydrocarbons such as butane, pentane, hexane, and heptane; aromatic hydrocarbons such as benzene, toluene, and xylene; and alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane, and decalin.

First, (a-1) is described as an organomagnesium complex soluble in an inert hydrocarbon solvent, but the relational expression n α +2 β ═ a + b + c, which includes dihydrocarbylmagnesium compounds and complexes of the compounds with other metal compounds, represents the valency of the metal atom and the stoichiometry of the substituent, in symbols α, β, a, b, and c.

In formula 2, as represented by R²And R³The hydrocarbon group having 2 to 20 carbon atoms is not particularly limited, and specific examples thereof include alkyl, cycloalkyl and aryl groups, such as ethyl, propyl, butyl, propyl, hexyl, octyl, decyl, cyclohexyl and phenyl groups, among which, when α > 0, the alkyl group is preferable, and the metal atom M is a metal atom¹Metal atoms belonging to any of groups 12, 13 and 14 of the periodic table of elements can be used, and examples thereof include zinc, boron, aluminum and the like. Among these, aluminum and/or zinc are preferable.

Magnesium relative to metal atom M¹The ratio of β/α is not particularly limited, but is preferablyPreferably 0.1 to 30 inclusive, more preferably 0.5 to 10 inclusive, and when a predetermined organomagnesium compound is used in which α ═ 0, for example, R is used²Such a compound is soluble in an inert hydrocarbon solvent in the case of 1-methylpropyl or the like, and also brings about satisfactory results in the present embodiment, in formula 2, R in the case where α is 0²And R³It is preferable that any of the three groups (1), (2), and (3) shown below is satisfied.

Group (1): preferably R²And R³At least one of them is a secondary or tertiary alkyl group having 4 to 6 carbon atoms, more preferably R²、R³All of which are alkyl groups having 4 to 6 carbon atoms and at least one of which is a secondary alkyl group or a tertiary alkyl group.

Group (2): preferably R²And R³Are alkyl groups having different carbon atoms, and R is more preferably²Is an alkyl group of 2 or 3 carbon atoms and R³An alkyl group having 4 or more carbon atoms.

Group (3): preferably R²And R³At least one of them is a hydrocarbon group having 6 or more carbon atoms, more preferably R²、R³The sum of the carbon atoms in the alkyl group (C) is 12 or more.

These groups are specifically shown below. In the group (1), specific examples of the secondary alkyl group or tertiary alkyl group having 4 to 6 carbon atoms include: 1-methylpropyl, 2-methylpropyl, 1-dimethylethyl, 2-methylbutyl, 2-ethylpropyl, 2-dimethylpropyl, 2-methylpentyl, 2-ethylbutyl, 2-dimethylbutyl, 2-methyl-2-ethylpropyl, etc. Among these, 1-methylpropyl group is preferable.

In the group (2), the alkyl group having 2 or 3 carbon atoms is not particularly limited, and specifically, there may be mentioned: ethyl, 1-methylethyl, propyl, and the like. Among these, ethyl is preferable. The alkyl group having 4 or more carbon atoms is not particularly limited, and specifically, there may be mentioned: butyl, pentyl, hexyl, heptyl, octyl and the like. Among these, butyl and/or hexyl are preferred.

In the group (3), the hydrocarbon group having 6 or more carbon atoms is not particularly limited, and specifically, there may be mentioned: hexyl, heptyl, octyl, nonyl, decyl, phenyl, 2-naphthyl, and the like. Among the hydrocarbon groups, alkyl groups are preferred, and among the alkyl groups, hexyl and/or octyl groups are more preferred.

In general, when the number of carbon atoms contained in the alkyl group is increased, the catalyst component tends to be easily dissolved in the inert hydrocarbon solvent, and the viscosity of the solution tends to be increased. Therefore, it is preferable to use long-length chain alkyl groups (the adaptation rate な long, for people suffering from stiff people アルキル). The organomagnesium compound may be diluted with an inert hydrocarbon solvent and used, but may be used without any problem even if a slight amount of a lewis basic compound such as ether, ester, or amine is contained or remains in the solution.

Then, for Y¹The description is given. In the formula 2, Y¹Represents alkoxy, siloxy, allyloxy, amino, amido, -N ═ C-R⁴、R⁵、-SR⁶(in these formulae, R⁴、R⁵And R⁶Each independently represents a hydrocarbon group having 2 to 20 carbon atoms) and β -keto acid residue.

In formula 2, as represented by R⁴、R⁵And R⁶The hydrocarbyl group represented by (a) is preferably an alkyl group or an aryl group having 1 to 12 carbon atoms, and more preferably an alkyl group or an aryl group having 3 to 10 carbon atoms. There are no particular restrictions, and specific examples include: methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 1-dimethylethyl, pentyl, hexyl, 2-methylpentyl, 2-ethylbutyl, 2-ethylpentyl, 2-ethylhexyl, 2-ethyl-4-methylpentyl, 2-propylheptyl, 2-ethyl-5-methyloctyl, octyl, nonyl, decyl, phenyl, naphthyl and the like. Among them, any of butyl, 1-methylpropyl, 2-methylpentyl and 2-ethylhexyl is preferable.

In formula 2, Y¹Preferably alkoxy or siloxy. The alkoxy group is not particularly limited, and specifically, methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, are preferableAny one of a phenyl group, a 1, 1-dimethylethoxy group, a pentyloxy group, a hexyloxy group, a 2-methylpentyloxy group, a 2-ethylbutoxy group, a 2-ethylpentyloxy group, a 2-ethylhexyloxy group, a 2-ethyl-4-methylpentyloxy group, a 2-propylheptyloxy group, a 2-ethyl-5-methyloctyloxy group, an octyloxy group, a phenoxy group, and a naphthyloxy group. Among these, any of butoxy, 1-methylpropoxy, 2-methylpentyloxy and 2-ethylhexyloxy is more preferable. The siloxy group is not particularly limited, and specifically, any of a hydrogendimethylsiloxy group, an ethylhydrogenmethylsiloxy group, a diethylhydrogensiloxy group, a trimethylsiloxy group, an ethyldimethylsiloxy group, a diethylmethylsiloxy group, and a triethylsiloxy group is preferable. Among these, any of a hydrogendimethylsiloxy group, an ethylhydrogenmethylsiloxy group, a diethylhydrogensiloxy group, and a trimethylsiloxy group is more preferable.

In the present embodiment, the method for synthesizing (A-1) is not particularly limited, and may be performed by using a compound belonging to the formula R²MgX¹And formula R² ₂Mg(R²As defined above, X¹Is halogen) and to a compound of formula M¹R³ _nAnd M¹R³ _(n-1)H(M¹And R³In the above sense, n represents M¹A valence of (b) in an inert hydrocarbon solvent at 25 ℃ to 150 ℃, followed by reacting with an organometallic compound represented by the formula Y¹-H(Y¹Is the aforementioned meaning) or with a compound having the formula Y¹An organomagnesium compound and/or an organoaluminum compound having the functional group shown above. Among these, in reacting an organomagnesium compound soluble in an inert hydrocarbon solvent with a compound represented by the formula Y¹In the case of reacting the compound represented by-H, the order of the reaction is not particularly limited, and addition of the compound represented by the formula Y to an organomagnesium compound may be used¹Method of preparing a compound represented by the formula Y¹A method of adding an organomagnesium compound to the compound represented by the formula-H, and a method of adding both at the same time.

In the present embodiment, Y in (A-1)¹The molar composition ratio c/(α + β) to all metal atoms is in the range of 0. ltoreq. c/(α + β). ltoreq.2, preferably 0. ltoreq. c/(α + β) < 1 through Y¹The reactivity of (A-1) to (A-2) tends to be improved when the molar composition ratio relative to all metal atoms is 2 or less.

Next, (A-2) will be explained. (A-2) is a titanium compound represented by formula 3.

(A-2)：Ti(OR⁷)_dX¹ _(4-d)Formula 3

(wherein d is a real number of 0 to 4, R⁷Is a hydrocarbon group of 1 to 20 carbon atoms, X¹Is a halogen atom. )

In formula 3, d is preferably 0 to 1, and d is more preferably 0. In formula 3, R represents⁷The hydrocarbon group represented is not particularly limited, and specifically, there may be mentioned: aliphatic hydrocarbon groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, 2-ethylhexyl, heptyl, octyl, decyl, and allyl; alicyclic hydrocarbon groups such as cyclohexyl, 2-methylcyclohexyl and cyclopentyl; aromatic hydrocarbon groups such as phenyl and naphthyl. Among these, aliphatic hydrocarbon groups are preferred. As a result of X¹Examples of the halogen include chlorine, bromine and iodine. Among these, chlorine is preferred. In the present embodiment, (A-2) is more preferably titanium tetrachloride. In the present embodiment, one or two or more compounds selected from the above compounds may be used alone or in combination.

Next, the reaction between (A-1) and (A-2) will be described. The reaction is preferably carried out in an inert hydrocarbon solvent, and more preferably in an aliphatic hydrocarbon solvent such as hexane or heptane. The molar ratio of (A-1) to (A-2) in the above reaction is not particularly limited, and the molar ratio of the Ti atom contained in (A-2) to the Mg atom contained in (A-1) (Ti/Mg) is preferably 0.1 or more and 10 or less, more preferably 0.3 or more and 3 or less. The reaction temperature is not particularly limited, but is preferably in the range of-80 ℃ to 150 ℃ inclusive, and more preferably in the range of-40 ℃ to 100 ℃. The order of addition of (A-1) and (A-2) is not particularly limited, and may be any of the methods of adding (A-2) after (A-1), adding (A-1) after (A-2), and simultaneously adding (A-1) and (A-2), and the method of simultaneously adding (A-1) and (A-2) is preferred. In the present embodiment, the solid catalyst component [ a ] obtained by the above reaction is used in the form of a slurry solution using an inert hydrocarbon solvent.

As another example of the Ziegler-Natta catalyst component used in the present embodiment, a catalyst for olefin polymerization comprising a solid catalyst component [ C ] produced by supporting an organomagnesium compound (C-4) soluble in an inert hydrocarbon solvent represented by the formula 6 and a titanium compound (C-5) represented by the formula 7 on a carrier (C-3) produced by the reaction of an organomagnesium compound (C-1) soluble in an inert hydrocarbon solvent represented by the formula 4 and a chlorinating agent (C-2) represented by the formula 5 and an organometallic compound component [ B ] is preferable.

(C-1)：(M²)_γ(Mg)_δ(R⁸)e(R⁹)_f(OR¹⁰)_gFormula 4

(in the formula, M²Is a metal atom belonging to any one of groups 12, 13 and 14 of the periodic Table of the elements, R⁸、R⁹And R¹⁰Each of the hydrocarbon groups having 2 to 20 carbon atoms, γ, δ, e, f and g is a real number satisfying the following relationship. 0. ltoreq. gamma.0.ltoreq.delta.0.ltoreq.e, 0. ltoreq.f, 0. ltoreq.g, 0. ltoreq.e + f, 0. ltoreq.g/(gamma + delta). ltoreq.2, k.gamma. + 2. delta. e + f + g (where k denotes M²The valence of (3). ))

(C-2)：H_hSiCl_iR¹¹ _(4-(h+i))… formula 5

(in the formula, R¹¹The hydrocarbon group having 1 to 12 carbon atoms, and h and i are real numbers satisfying the following relationship. H is more than 0, i is more than 0, h + i is more than 0 and less than or equal to 4)

(C-4)：(M¹)_α(Mg)_β(R²)_a(R³)_bY¹ _c… formula 6

(in the formula, M¹Is a metal atom belonging to any one of groups 12, 13 and 14 of the periodic Table of the elements, R²And R³Is the number of carbon atoms2 to 20 hydrocarbon groups, Y¹Is alkoxy, siloxy, allyloxy, amino, amido, -N ═ C-R⁴、R⁵、-SR⁶(in these formulae, R⁴、R⁵And R⁶A hydrocarbon group having 1 to 20 carbon atoms) and β -keto acid residue, in Y¹In the case of plural, Y¹α, β, a, b and c are real numbers satisfying the following relationships 0. ltoreq. α, 0 < β, 0. ltoreq. a, 0. ltoreq. b, 0. ltoreq. c, 0 < a + b, 0. ltoreq. b/(α + β). ltoreq.2, n α +2 β. ltoreq. a + b + c (here, n represents M)¹The valence of (3). ))

(C-5)：Ti(OR⁷)_dX¹ _(4-d)… formula 7

(wherein d is a real number of 0 to 4, R⁷Is a hydrocarbon group of 1 to 20 carbon atoms, X¹Is a halogen atom. )

First, (C-1) will be explained. (C-1) is shown in the form of an organomagnesium complex soluble in an inert hydrocarbon solvent, but contains all of the dihydrocarbylmagnesium compound and complexes of the compound with other metal compounds. The relationship k γ +2 δ ═ e + f + g of symbols γ, δ, e, f, and g in formula 4 represents the stoichiometry of the valence of the metal atom and the substituent.

In the above formula, from R⁸Or R⁹The hydrocarbon group represented is not particularly limited, and specifically, each is an alkyl group, a cycloalkyl group or an aryl group, and for example, there may be mentioned: methyl, ethyl, propyl, butyl, propyl, hexyl, octyl, decyl, cyclohexyl, phenyl, and the like. Among these, R is preferable⁸And R⁹Each is an alkyl group, in the case of α > 0, as the metal atom M²Metal atoms belonging to any of groups 12, 13 and 14 of the periodic table of elements can be used, and examples thereof include zinc, boron, aluminum and the like. Among these, aluminum and zinc are preferable.

Magnesium relative to metal atom M²The ratio δ/γ is not particularly limited, but is preferably 0.1 or more and 30 or less, and more preferably 0.5 or more and 10 or less. In addition, when a predetermined organomagnesium compound in which γ is 0 is usedUnder, for example, at R⁸In the case of 1-methylpropyl group or the like, it is soluble in an inert hydrocarbon solvent, and such a compound also brings about satisfactory results for the present embodiment. R in the case where γ is 0 in formula 4⁸、R⁹Preferably, the three groups (1), (2), and (3) are any of the following groups.

Group (1): r⁸、R⁹At least one of them is preferably a secondary or tertiary alkyl group having 4 to 6 carbon atoms, more preferably R⁸、R⁹All of which have 4 to 6 carbon atoms and at least one of which is a secondary alkyl group or a tertiary alkyl group.

Group (2): r⁸And R⁹Preferably, alkyl groups having different carbon atoms are used, and R is more preferably⁸Is alkyl of 2 or 3 carbon atoms, R⁹An alkyl group having 4 or more carbon atoms.

Group (3): r⁸And R⁹At least one of them is preferably a hydrocarbon group having 6 or more carbon atoms, more preferably R⁸And R⁹The sum of the carbon atoms in the alkyl group (C) is 12 or more.

The groups represented by these groups (1) to (3) are specifically shown below. In the group (1), specific examples of the secondary alkyl group or tertiary alkyl group having 4 to 6 carbon atoms include: 1-methylpropyl, 2-methylpropyl, 1-dimethylethyl, 2-methylbutyl, 2-ethylpropyl, 2-dimethylpropyl, 2-methylpentyl, 2-ethylbutyl, 2-dimethylbutyl, 2-methyl-2-ethylpropyl, etc. Among these, 1-methylpropyl group is preferable.

In the group (2), examples of the alkyl group having 2 or 3 carbon atoms include an ethyl group, a 1-methylethyl group, and a propyl group. Among these, ethyl is preferable. The alkyl group having 4 or more carbon atoms is not particularly limited, and specific examples thereof include butyl, pentyl, hexyl, heptyl, octyl, and the like. Among these, butyl and/or hexyl are preferred.

In the group (3), the hydrocarbon group having 6 or more carbon atoms is not particularly limited, and specific examples thereof include a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a phenyl group, and a 2-naphthyl group. Among the hydrocarbon groups, alkyl groups are preferred, and among the alkyl groups, hexyl and/or octyl groups are more preferred.

In general, when the number of carbon atoms contained in an alkyl group is increased, the alkyl group tends to be easily dissolved in an inert hydrocarbon solvent, and the viscosity of the solution tends to be increased. Therefore, it is preferable to use a medium-length chain alkyl group in terms of operation. The organomagnesium compound is used as an inert hydrocarbon solution, but may be used without any problem even if a slight amount of a lewis basic compound such as ether, ester, or amine is contained or remains in the solution.

Then, p-alkoxy (OR)¹⁰) The description is given. As a group consisting of R¹⁰The hydrocarbyl group represented by (a) is preferably an alkyl group or an aryl group having 1 to 12 carbon atoms, and more preferably an alkyl group or an aryl group having 3 to 10 carbon atoms. As R¹⁰There are no particular restrictions, and specific examples include: methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 1-dimethylethyl, pentyl, hexyl, 2-methylpentyl, 2-ethylbutyl, 2-ethylpentyl, 2-ethylhexyl, 2-ethyl-4-methylpentyl, 2-propylheptyl, 2-ethyl-5-methyloctyl, octyl, nonyl, decyl, phenyl, naphthyl and the like. Among these, any of butyl, 1-methylpropyl, 2-methylpentyl and 2-ethylhexyl is preferable.

In the present embodiment, the method for synthesizing (C-1) is not particularly limited, and the following methods are preferred: is represented by the formula R⁸MgX¹And formula R⁸ ₂Mg(R⁸As defined above, X¹Is a halogen atom) and an organomagnesium compound belonging to the group consisting of the compounds of the formula M²R⁹ _kAnd formula M²R⁹ _(k-1)H(M²、R⁹And k is as defined above) in an inert hydrocarbon solvent at a temperature of from 25 ℃ to 150 ℃, followed by reacting with an organometallic compound having the group consisting of R as required⁹(R⁹Is the aforementioned meaning) or an alcohol having a hydrocarbon group represented by R which is soluble in an inert hydrocarbon solvent⁹The alkoxy magnesium compound and/or alkoxy aluminum compound of the hydrocarbon group represented by (1).

Among these methods, in the case of reacting an organomagnesium compound soluble in an inert hydrocarbon solvent with an alcohol, the order of the reaction is not particularly limited, and any of a method of adding an alcohol to an organomagnesium compound, a method of adding an organomagnesium compound to an alcohol, or a method of adding both at the same time can be used. In the present embodiment, the reaction ratio of the organomagnesium compound soluble in the inert hydrocarbon solvent and the alcohol is not particularly limited, and as a result of the reaction, the molar composition ratio g/(γ + δ) of the alkoxy groups in the obtained alkoxy group-containing organomagnesium compound with respect to all the metal atoms is 0. ltoreq. g/(γ + δ). ltoreq.2, preferably 0. ltoreq. g/(γ + δ) < 1.

Next, (C-2) will be described. (C-2) is a silicon chloride compound having at least one Si-H bond represented by formula 5.

(C-2)：H_hSiCl_iR¹¹ _(4-(h+i))The chemical formula 5

(in the formula, R¹¹The hydrocarbon group having 1 to 12 carbon atoms, and h and i are real numbers satisfying the following relationship. H is more than 0, i is more than 0, h + i is more than 0 and less than or equal to 4)

In formula 5, from R¹¹The hydrocarbon group is not particularly limited, and specific examples thereof include aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups, and examples thereof include methyl groups, ethyl groups, propyl groups, 1-methylethyl groups, butyl groups, pentyl groups, hexyl groups, octyl groups, decyl groups, cyclohexyl groups, and phenyl groups. Among these, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a 1-methylethyl group is more preferable. Further, h and i are numbers larger than 0 satisfying the relationship of h + i.ltoreq.4, and i is preferably 2 to 3.

These compounds are not particularly limited, and specifically, there may be mentioned: HSiCl₃、HSiCl₂CH₃、HSiCl₂C₂H₅、HSiCl₂(C₃H₇)、HSiCl₂(2-C₃H₇)、HSiCl₂(C₄H₉)、HSiCl₂(C₆H₅)、HSiCl₂(4-Cl-C₆H₄)、HSiCl₂(CH＝CH₂)、HSiCl₂(CH₂C₆H₅)、HSiCl₂(1-C₁₀H₇)、HSiCl₂(CH₂CH＝CH₂)、H₂SiCl(CH₃)、H₂SiCl(C₂H₅)、HSiCl(CH₃)₂、HSiCl(C₂H₅)₂、HSiCl(CH₃)(2-C₃H₇)、HSiCl(CH₃)(C₆H₅)、HSiCl(C₆H₅)₂And the like. These chlorinated silicon compounds may be used singly or in combination of two or more. Among these, HSiCl is preferred₃、HSiCl₂CH₃、HSiCl(CH₃)₂、HSiCl₂(C₃H₇) More preferably HSiCl₃、HSiCl₂CH₃。

Next, the reaction between (C-1) and (C-2) will be described. In the reaction, it is preferable to use an inert hydrocarbon solvent, a chlorinated hydrocarbon such as1, 2-dichloroethane, o-dichlorobenzene, dichloromethane, etc.; ether media such as diethyl ether and tetrahydrofuran; or their mixed medium is used after (C-2) is diluted. Among these, inert hydrocarbon solvents are more preferable in terms of the performance of the catalyst. The reaction ratio of (C-1) and (C-2) is not particularly limited, and the silicon atom contained in (C-2) is preferably 0.01mol or more and 100mol or less, more preferably 0.1mol or more and 10mol or less, based on 1mol of the magnesium atom contained in (C-1).

The method of reacting (C-1) and (C-2) is not particularly limited, and any of a method of simultaneously introducing (C-1) and (C-2) into a reactor and reacting them, a method of introducing (C-1) into a reactor after (C-2) has been previously charged into a reactor, and a method of introducing (C-2) into a reactor after (C-1) has been previously charged into a reactor can be used. Among these, a method in which (C-2) is charged into a reactor in advance and then (C-1) is introduced into the reactor is preferred. The carrier (C-3) obtained by the above reaction is preferably separated by filtration or decantation, and then sufficiently washed with an inert hydrocarbon solvent to remove unreacted materials, by-products, and the like.

The reaction temperature of (C-1) and (C-2) is not particularly limited, but is preferably 0 ℃ or higher and 50 ℃ or lower, more preferably 3 ℃ or higher and 30 ℃ or lower, and still more preferably 5 ℃ or higher and 20 ℃ or lower. The reaction at a low temperature is preferable because particles of the carrier are likely to grow large. In the method of simultaneously adding (C-1) and (C-2) while introducing them into the reactor simultaneously for reaction, it is preferable to adjust the reaction temperature to a predetermined temperature by previously adjusting the temperature of the reactor to a predetermined temperature and adjusting the temperature in the reactor to a predetermined temperature while adding them simultaneously. In the method of introducing (C-1) into the reactor after (C-2) has been charged into the reactor in advance, it is preferable to adjust the reaction temperature to a predetermined temperature by adjusting the temperature of the reactor into which the silicon chloride compound has been charged to a predetermined temperature and adjusting the temperature inside the reactor to a predetermined temperature while introducing the organomagnesium compound into the reactor. In the method in which (C-1) is charged into a reactor in advance and then (C-2) is introduced into the reactor, the reaction temperature is adjusted to a predetermined temperature by adjusting the temperature of the reactor into which (C-1) is charged to a predetermined temperature and adjusting the temperature inside the reactor to a predetermined temperature while (C-2) is introduced into the reactor. The time for introducing (C-1) and (C-2) into the reactor is preferably 3 hours or more and 20 hours or less, more preferably 5 hours or more and 15 hours or less, and particularly preferably 7 hours or more and 13 hours or less. The reaction for a long time is preferable because particles of the carrier tend to grow large. The catalyst support produced by this method is generally larger than the support used in ziegler catalysts, and is intended to be intentionally left in the polyethylene powder after polymerization. By dissolving the polyethylene powder by the method described in examples, a polyethylene powder which is more easily dissolved than a usual polyethylene powder can be obtained because a large number of voids are formed in the interior.

Next, the organomagnesium compound (C-4) will be described. (C-4) is represented by the aforementioned formula 6.

(C-4)：(M¹)_α(Mg)_β(R²)_a(R³)_bY¹ _c… formula 6

(in the formula, M¹Is a metal atom belonging to any one of groups 12, 13 and 14 of the periodic Table of the elements, R²And R³A hydrocarbon group having 2 to 20 carbon atoms, Y¹Is alkoxy, siloxy, allyloxy, amino, amido, -N ═ C-R⁴、R⁵、-SR⁶(in these formulae, R⁴、R⁵And R⁶A hydrocarbon group having 1 to 20 carbon atoms) and β -keto acid residue, and when there are a plurality of Y1, Y is¹α, β, a, b and c are real numbers satisfying the following relationships 0. ltoreq. α, 0 < β, 0. ltoreq. a, 0. ltoreq. b, 0 < a + b, 0. ltoreq. b/(α + β). ltoreq.2, n α +2 β. ltoreq. a + b + c (where n represents M¹The valence of (3). ))

The amount of (C-4) used is preferably 0.1 to 10, more preferably 0.5 to 5, in terms of the molar ratio of the magnesium atom contained in (C-4) to the titanium atom contained in (C-5).

The reaction temperature of (C-4) and (C-5) is not particularly limited, but is preferably in the range of-80 ℃ to 150 ℃ inclusive, and more preferably in the range of-40 ℃ to 100 ℃ inclusive.

The concentration of (C-4) used is not particularly limited, but is preferably 0.1mol/L to 2mol/L, more preferably 0.5mol/L to 1.5mol/L, based on the titanium atom contained in (C-4). It is preferable to use an inert hydrocarbon solvent for the dilution of (C-4).

The order of adding (C-4) and (C-5) to (C-3) is not particularly limited, and any of a method of adding (C-5) after (C-4), a method of adding (C-4) after (C-5), and a method of adding (C-4) and (C-5) simultaneously may be used. Among these, a method of adding (C-4) and (C-5) simultaneously is preferred. The reaction of (C-4) and (C-5) is carried out in an inert hydrocarbon solvent, preferably an aliphatic hydrocarbon solvent such as hexane or heptane. The catalyst thus obtained is used as a slurry solution using an inert hydrocarbon solvent.

Next, (C-5) will be described. In the present embodiment, (C-5) is a titanium compound represented by the aforementioned formula 7.

(C-5)：Ti(OR⁷)_dX¹ _(4-d)Formula 7

(wherein d is a real number of 0 to 4, R⁷Is a hydrocarbon group of 1 to 20 carbon atoms, X¹Is a halogen atom. )

As represented by R in formula 7⁷The hydrocarbon group represented is not particularly limited, and specifically, there may be mentioned: aliphatic hydrocarbon groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, 2-ethylhexyl, heptyl, octyl, decyl, and allyl; alicyclic hydrocarbon groups such as cyclohexyl, 2-methylcyclohexyl and cyclopentyl; aromatic hydrocarbon groups such as phenyl and naphthyl. Among these, aliphatic hydrocarbon groups are preferable. As a result of X¹The halogen represented is not particularly limited, and specifically, chlorine, bromine and iodine are exemplified. Among these, chlorine is preferred. The compounds selected from the above (C-5) may be used singly or in combination of two or more.

The amount of (C-5) used is not particularly limited, but is preferably 0.01 to 20, more preferably 0.05 to 10 in terms of a molar ratio to the magnesium atom contained in the carrier (C-3).

The reaction temperature of (C-5) is not particularly limited, but is preferably in the range of-80 ℃ to 150 ℃, more preferably-40 ℃ to 100 ℃. In the present embodiment, the method for supporting (C-5) on (C-3) is not particularly limited, and a method of reacting an excess of (C-5) with (C-3), a method of efficiently supporting (C-5) by using the third component, and preferably a method of supporting (C-5) by reaction with the organomagnesium compound (C-4) may be used.

Next, the organometallic compound constituent [ B ] in the present embodiment will be described. The solid catalyst component of the present embodiment is a highly active polymerization catalyst by combining with the organometallic compound component [ B ]. The organometallic compound component [ B ] is sometimes also referred to as a "cocatalyst". The organometallic compound component [ B ] is preferably a compound containing a metal belonging to any of groups 1,2, 12 and 13 of the periodic table, and particularly preferably an organoaluminum compound and/or an organomagnesium compound.

As the organoaluminum compound, a compound represented by the following formula 8 is preferably used alone or in combination.

AlR¹² _jZ¹ _(3-j)… formula 8

(in the formula, R¹²A hydrocarbon group having 1 to 20 carbon atoms, Z¹Is a group belonging to the group consisting of hydrogen, halogen, alkoxy, allyloxy, and siloxy, and j is a number of 2 to 3. )

In the above formula 8, R is represented by¹²The hydrocarbon group having 1 to 20 carbon atoms is not particularly limited, and specifically includes any of aliphatic hydrocarbons, aromatic hydrocarbons, and alicyclic hydrocarbons. As the compound represented by formula 8, for example, preferred are: trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, tris (2-methylpropyl) aluminum (or triisobutylaluminum), tripentylaluminum, tris (3-methylbutyl) aluminum, trihexylaluminum, trioctylaluminum, and tridecylaluminum; aluminum halide compounds such as diethylaluminum chloride, ethylaluminum dichloride, bis (2-methylpropyl) aluminum chloride, ethylaluminum sesquichloride and diethylaluminum bromide; alkoxy aluminum compounds such as diethyl aluminum ethoxide and di (2-methylpropyl) aluminum butoxide; siloxy aluminum compounds such as dimethylhydrogensiloxy dimethylaluminum, ethylmethylhydrosiloxy diethylaluminum, and ethyldimethylsiloxy diethylaluminum; and mixtures thereof. Among these, trialkylaluminum compounds are more preferred.

As the organomagnesium compound, an organomagnesium compound represented by formula 4 that is soluble in an inert hydrocarbon solvent is preferable.

(M²)_γ(Mg)_δ(R⁸)_e(R⁹)_f(OR¹⁰)_gFormula 4

(in the formula, M²Is a metal atom belonging to any one of groups 12, 13 and 14 of the periodic Table of the elements, R⁸、R⁹And R¹⁰Each is a hydrocarbon group having 2 to 20 carbon atoms, and γ, δ, e, f and g are real numbers satisfying the following relationship.0. ltoreq. gamma.0.ltoreq.delta.0.ltoreq.e, 0. ltoreq.f, 0. ltoreq.g, 0. ltoreq.e + f, 0. ltoreq.g/(gamma + delta). ltoreq.2, k.gamma. + 2. delta. e + f + g (where k denotes M²The valence of (3). ))

The organomagnesium compound is shown in the form of an organomagnesium complex that is soluble in an inert hydrocarbon solvent, but includes the entirety of the dialkylmagnesium compound and complexes of the compound with other metal compounds. Regarding gamma, delta, e, f, g, M²、R⁸、R⁹、OR¹⁰As described above, the organomagnesium compound is preferably highly soluble in an inert hydrocarbon solvent, and therefore β/α is preferably in the range of 0.5 to 10, and M is more preferably²Is a compound of aluminum.

The method for adding the solid catalyst component and the organometallic compound component [ B ] to the polymerization system under polymerization conditions is not particularly limited, and both may be added to the polymerization system separately or may be added to the polymerization system after reacting both in advance. The ratio of the two components to be combined is not particularly limited, and the organometallic compound component [ B ] is preferably 1 to 3000mmol relative to 1g of the solid catalyst component.

The metallocene catalyst of the present embodiment is not particularly limited, and is preferably a supported constrained geometry metallocene catalyst prepared from at least a (a) support material (hereinafter, also referred to as "component (a)", "(b)" an organoaluminum compound (hereinafter, also referred to as "component (b)", "(b)"), (c) a transition metal compound having a cyclic η -bonded anionic ligand (hereinafter, also referred to as "component (c)", "(c)"), and (d)) an activator capable of reacting with the transition metal compound having a cyclic η -bonded anionic ligand to form a complex exhibiting catalytic activity (hereinafter, also referred to as "component (d)", "(d)").

The (A) carrier substance is not particularly limited, and examples thereof include (co) polymers of α -olefins having 2 to 10 carbon atoms, (co) polymers of α -olefins having 2 to 10 carbon atomsExamples of the polymer include: polyethylene, polypropylene, polybutene-1, ethylene-propylene copolymers, ethylene-butene-1 copolymers, ethylene-hexene-1 copolymers, propylene-butene-1 copolymers, propylene-divinylbenzene copolymers; aromatic unsaturated hydrocarbon polymers such as polystyrene, styrene-divinylbenzene copolymer; and polar group-containing polymers such as polyacrylates, polymethacrylates, polyacrylonitrile, polyvinyl chloride, polyamides and polycarbonates. The inorganic carrier is not particularly limited, and examples thereof include: SiO 2₂、Al₂O₃、MgO、TiO₂、B₂O₃、CaO、ZnO、BaO、ThO、SiO₂-MgO、SiO₂-Al₂O₃、SiO₂-V₂O₅And the like inorganic oxides; MgCl₂、AlCl₃、MnCl₂And inorganic halogen compounds; na (Na)₂CO₃、K₂CO₃、CaCO₃、MgCO₃、Al₂(SO₄)₃、BaSO₄、KNO₃、Mg(NO₃)₂And inorganic carbonates, sulfates, and nitrates; mg (OH)₂、Al(OH)₃、Ca(OH)₂And the like. Among these, the preferred support material is SiO₂. The particle size of the carrier material may be set to any value, and is preferably 1.0 μm or more and 100 μm or less, more preferably 2.0 μm or more and 50 μm or less, and still more preferably 3.0 μm or more and 10 μm or less.

The (A) support material is preferably treated with (B) an organoaluminum compound as required. The preferable (B) organoaluminum compound is not particularly limited, and examples thereof include: alkylaluminums such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum and trioctylaluminum; alkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride; aluminum alkoxides such as diethylaluminum ethoxide and dimethylaluminum methoxide; aluminoxanes such as methylaluminoxane, isobutylaluminoxane and methylisobutylaluminoxane. Among these, trialkylaluminums and aluminum alkoxides are preferable, and trimethylaluminum, triethylaluminum, and triisobutylaluminum are more preferable.

The supported constrained geometry metallocene catalyst may contain (c) a transition metal compound having a cyclic η -bonded anionic ligand (hereinafter, also simply referred to as "transition metal compound"). the transition metal compound of the present embodiment is not particularly limited, and may be represented by, for example, the following formula 9.

L_lMX_pX’_q… formula 9

In formula 9, M represents a transition metal belonging to group 4 of the periodic table of the elements, which has an oxidation number of +2, +3, or +4, and which is η 5-bonded to 1 or more ligands L.

In formula 9, L each independently represents a cyclic η -bonded anionic ligand, the cyclic η -bonded anionic ligand is cyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl or octahydrofluorenyl, which groups may optionally have 1 to 8 substituents each independently selected from the group consisting of hydrocarbyl, halogen, halogenated hydrocarbyl, aminohydrocarbyl, hydrocarbyloxy, dihydrocarbylamino, hydrocarbylphosphino, silyl, aminosilyl, hydrocarbyloxysilyl and halogenated silyl containing not more than 20 non-hydrogen atoms, and further 2L may be bonded by a 2-valent substituent such as hydrocarbadiyl, halogenated hydrocarbadiyl, hydrocarbyleneoxy, hydrocarbyleneamino, silandiyl, halosiladiyl or aminosilyl containing not more than 20 non-hydrogen atoms.

In formula 9, X each independently represents an anionic σ -bonded ligand having a valence of 1 having not more than 60 non-hydrogen atoms, an anionic σ -bonded ligand having a valence of 2 bonded to M, or an anionic σ -bonded ligand having a valence of 2 bonded to M and L each having a valence of 1. X' each independently represents a neutral Lewis base coordinating compound selected from the group consisting of phosphines having 4 to 40 carbon atoms, ethers, amines, olefins, and conjugated dienes.

In formula 9, l represents an integer of 1 or 2. p represents an integer of 0, 1 or 2, and when X represents an anionic σ -bonded ligand having a valence of 1 or an anionic σ -bonded ligand having a valence of 2, which is bonded to M and L at a valence of 1, respectively, p represents an integer of L or more less in formal oxidation number than M, and when X represents an anionic σ -bonded ligand having a valence of 2, which is bonded to M at a valence of 2, p represents an integer of L +1 or more less in formal oxidation number than M. Further, q represents an integer of 0, 1 or 2. The transition metal compound is preferably a compound represented by formula 9 wherein l represents 1.

A preferable example of the transition metal compound is a compound represented by the following formula 10.

In formula 10, M represents titanium, zirconium or hafnium of formula oxidation number +2, +3 or + 4. In formula 10, R is¹Each independently represents hydrogen, hydrocarbyl, silyl, germyl, cyano, halogen, or a complex thereof, which may each have no more than 20 non-hydrogen atoms, and further, adjacent R¹They may be bonded to each other to form a 2-valent derivative such as a hydrocarbadiyl group, a silanediyl group, or a germadidiyl group, and may be cyclic.

In the formula 10, X 'each independently represents a halogen, a hydrocarbon group, a hydrocarbon oxy group, a hydrocarbon amino group or a silyl group, each of which has not more than 20 non-hydrogen atoms, and 2X' may form a neutral conjugated diene having 5 to 30 carbon atoms or a 2-valent derivative. Y represents-O-, -S-, -NR³-or-PR³-, Z represents SiR³ ₂、CR³ ₂、SiR³ ₂SiR³ ₂、CR³ ₂CR³ ₂、CR³＝CR³、CR³ ₂SiR³ ₂Or GeR³ ₂Where R is³Each independently represents an alkyl group having 1 to 12 carbon atoms or an allyl group. In addition, n represents an integer of 1 to 3.

More preferable examples of the transition metal compound include compounds represented by the following formula 11 and the following formula 12.

In formulae 11 and 12, respectively, R¹Each independently represents hydrogen, hydrocarbyl, silyl, germyl, cyano, halogen, or a complex thereof, and may each have no more than 20 non-hydrogen atoms. Further, M represents titanium, zirconium or hafnium. Z, Y, X and X' represent the same groups as those represented in formula 10.

In formulae 11 and 12, p represents 0, 1 or 2, and q represents 0 or 1, respectively. When p represents 2 and q represents 0, the oxidation number of M is +4 and X is a halogen, a hydrocarbon group, a hydrocarbyloxy group, a dihydrocarbylamino group, a dihydrocarbylphosphite group, a hydrocarbyl sulfide group, a silyl group, or a complex thereof, and represents a group having not more than 20 non-hydrogen atoms.

In formulae 11 and 12, respectively, when p represents 1 and q represents 0, the oxidation number of M is +3 and X represents a stabilizing anionic ligand selected from allyl, 2- (N, N-dimethylaminomethyl) phenyl and 2- (N, N-dimethyl) -aminobenzyl; or a derivative of a conjugated diene in which the oxidation number of M is +4 and X represents a valence of 2; or M and X together form a metal cyclopentenyl group.

In each of formulae 11 and 12, when p represents 0 and q represents 1, the conjugated or non-conjugated diene in which the oxidation number of M is +2 and X 'is neutral may be optionally substituted with 1 or more hydrocarbon groups, and X' may contain not more than 40 carbon atoms and form a pi-type complex with M.

Further preferable examples of the transition metal compound include compounds represented by the following formulae 13 and 14.

In formulae 13 and 14, respectively, R¹Each independently represents hydrogen or an alkyl group having 1 to 6 carbon atoms. In addition, M represents titanium, Y represents-O-, -S-,-NR³-、-PR³-. Z represents SiR³ ₂、CR³ ₂、SiR³ ₂SiR³ ₂、CR³ ₂CR³ ₂、CR³＝CR³、CR³ ₂SiR^3- ₂Or GeR³ ₂，R³Each independently represents hydrogen, or a hydrocarbon group, a hydrocarbyloxy group, a silyl group, a haloalkyl group, a haloalkenyl group or a complex group thereof, which may have not more than 20 non-hydrogen atoms, and further, as required, 2R's in Z³Each other or R in Z³And R in Y³Can be bonded to each other to form a ring.

In formulae 13 and 14, p represents 0, 1 or 2, and q represents 0 or 1, respectively. Wherein, when p represents 2 and q represents 0, the oxidation number of M is +4 and each X independently represents a methyl group or a benzyl group. When p represents 1 and q represents 0, the oxidation number of M is +3 and X represents 2- (N, N-dimethyl) aminobenzyl, or the oxidation number of M is +4 and X represents 2-butene-1, 4-diyl. In addition, when p represents 0 and q represents 1, the oxidation number of M is +2 and X' represents 1, 4-diphenyl-1, 3-butadiene or 1, 3-pentadiene. These dienes are exemplified by asymmetric dienes which form a metal complex, and are actually a mixture of geometric isomers.

The supported constrained geometry metallocene catalyst comprises (D) an activator capable of reacting with a transition metal compound to form a complex exhibiting catalytic activity (hereinafter, also simply referred to as "activator"). In general, in metallocene catalysts, a transition metal compound and a complex formed from the above activator exhibit high olefin polymerization activity as a catalytically active material. In the present embodiment, the activator is not particularly limited, and examples thereof include a compound represented by the following formula 15.

[L-H]^d+[M_mQ_p]^d-… formula 15

In the formula 15, [ L-H ]]^d+Represents a bronsted acid which donates protons, and Li represents a neutral lewis base. In addition, [ M ]_mQ_p]^d-Representing a phaseA compatible non-coordinating anion, M represents a metal or metalloid selected from groups 5 to 15 of the periodic Table of the elements, Q each independently represents a hydride, dialkylamino, halide, alkoxy, allyloxy, hydrocarbon or substituted hydrocarbon having not more than 20 carbon atoms, and Q as a halide is 1 or less. M represents an integer of 1 to 7, p represents an integer of 2 to 14, d represents an integer of 1 to 7, and p-m ═ d.

A more preferred example of the activator is a compound represented by formula 16 below.

[L-H]^d+[M_mQ_n(G_q(T-H)_r)_Z]^d-… formula 16

In the formula 16, [ L-H ]]^d+Represents a bronsted acid which donates protons, and L represents a neutral lewis base. In addition, [ M ]_mQ_n(G_q(T-H)_r)_Z]^d-M represents a metal or metalloid selected from groups 5 to 15 of the periodic Table of the elements, Q each independently represents a hydride, a dialkylamino group, a halide, an alkoxy group, an allyloxy group, a hydrocarbon group, or a substituted hydrocarbon group having not more than 20 carbon atoms, and Q as a halide is 1 or less. In addition, G represents a polyvalent hydrocarbon group having a valence of r +1 bonded to M and T, and T represents O, S, NR or PR. Wherein R represents a hydrocarbon group, a trihydrocarbylsilyl group, a trihydrocarbylgermyl group or hydrogen. M represents an integer of 1 to 7, n represents an integer of 0 to 7, q represents an integer of 0 or 1, r represents an integer of 1 to 3, z represents an integer of 1 to 8, d represents an integer of 1 to 7, and n + z-m is d.

A further preferable example of the activator is a compound represented by the following formula 17.

[L-H]⁺[BQ₃Q¹]^-Control formula 17

In the formula 17, [ L-H ]]⁺Represents a bronsted acid which donates protons, and L represents a neutral lewis base. In addition, [ BQ₃Q¹]^-Represents a compatible non-coordinating anion, B represents boron, and Q independently represents pentafluorophenyl or Q¹Denotes having 1 OH group as a substituentA substituted allyl group having 6 to 20 carbon atoms.

The proton donating bronsted acid is not particularly limited, and examples thereof include: trialkyl-substituted ammonium cations such as triethylammonium, tripropylammonium, tri (n-butyl) ammonium, trimethylammonium, tributylammonium, tri (n-octyl) ammonium, diethylmethylammonium, dibutylmethylammonium, dibutylethylammonium, dihexylmethylammonium, dioctylmethylammonium, didecylmethylammonium, didodecylmethylammonium, ditetradecylmethylammonium, dihexadecylmethylammonium, dioctadecylmethylammonium, dieicosylmethylammonium and bis (hydrogenated tallow alkyl) methylammonium; n, N-dimethylaniline

N, N-diethylaniline

N, N-2,4, 6-pentamethylbenzamines

And N, N-dimethylbenzylaniline

iso-N, N-dialkylanilines

A cation; trityl cation.

The compatible non-coordinating anion is not particularly limited, and examples thereof include: triphenyl (hydroxyphenyl) borate, diphenylbis (hydroxyphenyl) borate, triphenyl (2, 4-dihydroxyphenyl) borate, tris (p-tolyl) (hydroxyphenyl) borate, tris (pentafluorophenyl) (hydroxyphenyl) borate, tris (2, 4-dimethylphenyl) (hydroxyphenyl) borate, tris (3, 5-dimethylphenyl) (hydroxyphenyl) borate, tris (3, 5-bis (trifluoromethylphenyl)) (hydroxyphenyl) borate, tris (pentafluorophenyl) (2-hydroxyethyl) borate, tris (pentafluorophenyl) (4-hydroxybutyl) borate, tris (pentafluorophenyl) (4-hydroxycyclohexyl) borate, tris (pentafluorophenyl) (4- (4' -hydroxyphenyl) phenyl) borate and tris (pentafluorophenyl) (6-hydroxy-2-naphthyl) borate. These compatible noncoordinating anions are also referred to as "borate compounds". The activator of the supported constrained geometry metallocene catalyst is preferably a borate compound from the viewpoint of catalytic activity and from the viewpoint of reducing the total content of Al, Mg, Ti, Zr, and Hf. A preferable borate compound includes tris (pentafluorophenyl) (hydroxyphenyl) borate.

As the activator, an organometallic oxy compound having a unit represented by the following formula 18 can be used.

(in formula 18, M²Represents a metal or metalloid of group 13 to group 15 of the periodic Table of the elements, R independently represents a hydrocarbon or substituted hydrocarbon group having 1 to 12 carbon atoms, and n represents a metal M²M represents an integer of 2 or more. )

Other preferable examples of the activator are organoaluminum oxy-compounds containing a unit represented by the following formula 19.

(in the formula 19, R represents C1-8 alkyl, m represents 2-60 integer.)

A more preferred example of the activator is methylaluminoxane comprising a unit represented by the following formula 20.

(in formula 20, m represents an integer of 2-60.)

In addition to the components (A) to (D), an organoaluminum compound may be used as a catalyst, if necessary. The organoaluminum compound is not particularly limited, and examples thereof include compounds represented by the following formula 21.

AlR_nX_3-n… formula 21

In the formula 21, R represents a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms or an allyl group having 6 to 20 carbon atoms, X represents a halogen, hydrogen or alkoxy group, and n represents an integer of 1 to 3. In addition, the organoaluminum compound may be a mixture of the compounds represented by formula 21.

The catalyst can be obtained by supporting the component (b), the component (c), and the component (d) on the component (a). The method for supporting the component (b), the component (c), and the component (d) is not particularly limited, and examples thereof include: a method in which the component (b), the component (c), and the component (d) are dissolved in respective soluble inert solvents, mixed with the component (a), and then the solvent is distilled off; a method in which the component (b), the component (c), and the component (d) are dissolved in an inert solvent, then concentrated in a range in which a solid does not precipitate, and then the component (a) is added in an amount capable of keeping the total amount of the concentrated solution in particles; a method of loading the component (B) and the component (D) on the component (A) first, followed by loading the component (C); a method in which the component (B), the component (D) and the component (C) are supported on the component (A) in this order. The component (c) and the component (d) in the present embodiment are preferably liquid or solid. The component (b), the component (c), and the component (d) may be used by diluting them in an inert solvent at the time of loading.

The inert solvent is not particularly limited, and examples thereof include: aliphatic hydrocarbons such as isobutane, pentane, hexane, heptane, octane, decane, dodecane, kerosene, and the like; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; mixtures thereof. The inert solvent is preferably used by removing impurities such as water, oxygen, and sulfur using a drying agent, an adsorbent, or the like. The amount of the component (B) is preferably 1.0X 10 in terms of Al atom to 1.0g of the component (A)^-5mol～1.0×10^{- 1}mol, more preferably 1.0X 10^-4mol～5.0×10^-2mol, component (C) is preferably 1.0X 10^-7mol～1.0×10^{- 3}mol, more preferably 5.0X 10^-7mol～5.0×10^-4mol, the component (D) is preferably 1.0X 10^-7mol～1.0×10^{- 3}mol, more preferably 5.0X 10^-7mol～5.0×10^-4The range of mol. The amount of each component used and the method of loading are determined in accordance with the activity, economy, powder characteristics, and fouling in the reactor. The supported constrained geometry metallocene catalyst thus obtained may be washed with an inert solvent by decantation, filtration or the like for removing the organoaluminum compound, borate compound or titanium compound which is not supported on the carrier.

The series of operations such as dissolution, contact, washing and the like are preferably carried out at a temperature of-30 ℃ or higher and 80 ℃ or lower selected for each unit operation. A more preferable range of such temperature is 0 ℃ or more and 50 ℃ or less. In addition, the series of operations to obtain the supported constrained geometry metallocene catalyst is preferably carried out in an inert atmosphere after drying.

The supported constrained geometry metallocene catalyst can be used alone for homopolymerization of ethylene or copolymerization of ethylene and α -olefin, but it may be used in the presence of an organoaluminum compound as an additional component in order to prevent poisoning of the solvent or reaction.

[ Process for producing ethylene Polymer ]

The polymerization method in the method for producing an ethylene-based polymer of the present embodiment may be a method of (co) polymerizing ethylene or a monomer containing ethylene by a suspension polymerization method or a gas phase polymerization method. Among these, the suspension polymerization method which can effectively remove the heat of polymerization is preferable. In the suspension polymerization process, it is possible to use an inert hydrocarbon medium as medium and also to use the olefin itself as solvent.

The inert hydrocarbon medium is not particularly limited, and specifically, there may be mentioned: aliphatic hydrocarbons such as propane, butane, isobutane, pentane, isopentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as ethyl chloride, chlorobenzene, and dichloromethane, and mixtures thereof.

The polymerization temperature in the method for producing an ethylene polymer of the present embodiment is usually preferably 30 ℃ to 100 ℃, more preferably 35 ℃ to 90 ℃, and still more preferably 40 ℃ to 80 ℃. If the polymerization temperature is 30 ℃ or higher, the polymer can be produced industrially efficiently. On the other hand, if the polymerization temperature is 100 ℃ or lower, stable operation can be continuously performed.

The polymerization pressure in the method for producing an ethylene polymer of the present embodiment is generally preferably normal pressure or more and 2MPa or less, more preferably 0.1MPa or more and 1.5MPa or less, and still more preferably 0.1MPa or more and 1.0MPa or less.

By increasing the amount of comonomer during the polymerization reaction, the comonomer rich component can be distributed inhomogeneously inside the polyethylene powder. This is preferable because the central portion of the powder, which is likely to be left dissolved, is likely to be dissolved in the liquid paraffin, and therefore, defects are less likely to occur. Further, the powder is preferably dissolved easily in the center portion, because the dissolution rate is also increased.

In order to increase the amount of the comonomer during the polymerization reaction, a batch type or a continuous type using a plurality of polymerizers is preferable as the form of the polymerization. It is particularly preferred to carry out the polymerization in a continuous manner. By continuously supplying ethylene gas, a solvent, a catalyst, etc. into the polymerization system and continuously discharging the ethylene gas together with the produced ethylene polymer, a local high-temperature state due to a rapid reaction of ethylene can be suppressed, and the polymerization system can be stabilized. When ethylene is reacted in a homogeneous state in the system, the formation of a branch chain, a double bond, or the like in the polymer chain is suppressed, or the formation of a low molecular weight component or an ultrahigh molecular weight material due to decomposition or crosslinking of the ethylene polymer is suppressed, and the crystalline component of the ethylene polymer is easily formed. This makes it easy to obtain a crystalline component in an amount sufficient for the strength of a film, microporous film, or the like. Therefore, a more uniform continuous type in the polymerization system is preferred.

The molecular weight of the ethylene polymer can be adjusted by, for example, allowing hydrogen to be present in the polymerization system or changing the polymerization temperature, as described in the west de patent application publication No. 3127133. By adding hydrogen as a chain transfer agent to the polymerization system, the molecular weight can be controlled within an appropriate range. When hydrogen is added to the polymerization system, the mole fraction of hydrogen is preferably 0 mol% or more and 30 mol% or less, more preferably 0 mol% or more and 25 mol% or less, and still more preferably 0 mol% or more and 20 mol% or less.

Further, it is preferable that hydrogen gas is previously brought into contact with the catalyst and then added to the polymerization system from the catalyst introduction pipe. Immediately after the catalyst is introduced into the polymerization system, the possibility that ethylene rapidly reacts due to the high catalyst concentration near the outlet of the introduction pipe to be in a locally high temperature state is increased, but by bringing hydrogen gas and the catalyst into contact before introducing them into the polymerization system, the initial activity of the catalyst can be suppressed, and side-products and the like which inhibit the production of crystalline components can also be suppressed. Therefore, it is preferable to introduce hydrogen into the polymerization system in a state of contacting with the catalyst.

For the same reason, the outlet of the catalyst-introducing pipe in the polymerization system is preferably disposed as far as possible from the outlet of the ethylene-introducing pipe. Specifically, there may be mentioned a method of introducing ethylene from the bottom of the polymerization liquid and introducing a catalyst from the middle between the liquid surface and the bottom of the polymerization liquid.

The solvent separation method in the method for producing an ethylene-based polymer according to the present embodiment may be performed by a decantation method, a centrifugation method, a filter filtration method, or the like, and a centrifugation method having a good separation efficiency between the ethylene-based polymer and the solvent is more preferable. The amount of the solvent contained in the ethylene-based polymer after the separation of the solvent is not particularly limited, and is 70% by mass or less, more preferably 60% by mass or less, and still more preferably 50% by mass or less, relative to the weight of the ethylene-based polymer. When the solvent contained in the ethylene polymer is dried and removed in a small amount, the metal component, the low molecular weight component and the like contained in the solvent tend not to remain in the ethylene polymer. Since crystalline components of the ethylene polymer are easily produced without leaving these components, a crystalline component in an amount sufficient for the strength of a film, a microporous film, or the like can be easily obtained. Therefore, it is preferable to separate the ethylene polymer from the solvent by a centrifugal separation method.

The method of deactivating the catalyst used for synthesizing the ethylene polymer of the present embodiment is not particularly limited, and it is preferably carried out after separating the ethylene polymer from the solvent. By introducing a chemical agent for deactivating the catalyst after separation from the solvent, precipitation of low molecular weight components, catalyst components, and the like contained in the solvent can be reduced.

Examples of the chemical agent for deactivating the catalyst system include oxygen, water, alcohols, glycols, phenols, carbon monoxide, carbon dioxide, ethers, carbonyl compounds, alkynes, and the like.

The drying temperature in the method for producing an ethylene polymer of the present embodiment is usually preferably 50 ℃ to 150 ℃, more preferably 50 ℃ to 140 ℃, and still more preferably 50 ℃ to 130 ℃. If the drying temperature is 50 ℃ or higher, effective drying can be performed. On the other hand, if the drying temperature is 150 ℃ or lower, the ethylene polymer can be dried in a state in which decomposition and crosslinking of the ethylene polymer are suppressed. In the present embodiment, other known components useful for producing an ethylene-based polymer may be contained in addition to the above-described components.