JP2004182971A - Improved method for producing polyolefin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To embody efficient industrialization in a large-scale olefin polymerization with a metallocene catalyst, in which the embodiment comprises raising catalytic activity and polymerization efficiency, fully showing a metallocene catalyst capability, and maintaining a stable polymerization reaction. <P>SOLUTION: In a commercial scale production plant of the olefin polymerization with the metallocene catalyst, an improved method for producing the polyolefin comprises controlling a content of inclusion of a halogen-containing compound to a gram atomic weight of a transition metal of the metallocene catalyst becoming ≤0.8, the content of inclusion of a halogen-containing compound meaning a gram atomic weight of the halogen atom in a halogen-containing compound derived from a solvent, a raw material, and the like except the halogen atom derived from the catalyst components. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

  The present invention relates to an improvement in a method for producing a polyolefin by polymerizing an olefin using a single-site catalyst, and more particularly, to an improvement in a method for polymerizing a polyolefin using a metallocene catalyst comprising a metallocene complex and a co-catalyst to improve the performance of the metallocene catalyst. The present invention relates to a method for polymerizing a polyolefin, in which the above-mentioned is fully exhibited and a stable polymerization reaction is maintained.

Polyolefins such as polyethylene and polypropylene are excellent in mechanical properties, chemical resistance, etc., and have a very good balance between their properties and economics. It is widely used as a material.
Conventionally, these polyolefins are mainly produced by using a so-called Ziegler-Natta catalyst in which a titanium trichloride, a titanium tetrachloride, or a transition metal catalyst in which these are supported on a carrier such as magnesium chloride and an organic aluminum compound are combined. Has been produced as a polyolefin having excellent physical properties and stereoregularity. Improvements in catalytic activity, stereoregularity, and the like have been continued by using various types of supports, electron donors, and organic silicon compounds.

On the other hand, unlike the Ziegler-Natta catalyst, which is a multi-site catalyst, a so-called metallocene catalyst, which is a single-site catalyst in which a metal transition metal complex in which a cyclopentadienyl ring or the like is coordinated with a metal atom and a promoter such as aluminoxane are combined A method for producing a polyolefin in which an olefin is polymerized using a system catalyst has been developed, and has recently attracted more attention than a polymerization method using a Ziegler-Natta catalyst.
This is because the metallocene-based catalyst is soluble in organic solvents, enables homogeneous polymerization, has very high catalytic activity, brings a unique stereoregularity, and can produce a high-molecular-weight polyolefin having a narrow molecular weight distribution. Improvements and developments in ligands and their substituents and transition metals or cocatalysts as well as in supports have been continued, and third components such as expensive aluminoxane cocatalysts and organoaluminum compounds have also been developed. . Further, the metallocene-based catalyst is also capable of polymerizing higher olefins, cyclic olefins, polar monomers, and the like.

  As described above, metallocene-based catalysts are generally recognized as important and extremely innovative catalysts in the polymerization of polyolefins.However, they can be applied to heterogeneous reactions such as slurry polymerization, and can replace expensive aluminoxane. There are also many problems to be solved, such as the development of materials or the reduction of sensitive catalytic activity due to impurities. In particular, metallocene-based catalysts are more sensitive to impurities in the polymerization reaction system than Ziegler-type catalysts, and therefore, strict control and management of raw materials such as monomers and catalysts and impurities in the polymerization reaction system are strictly required. Has become a bottleneck for large-scale and efficient industrialization of olefin polymerization.

  Numerous improvement proposals have been made with the aim of improving such problems to the industrialization of metallocene catalysts, for example, using silica-supported methylaluminoxane as an adaptation to heterogeneous reactions (see Patent Document 1). And non-coordinating boron compounds of Lewis acids as substitutes for expensive aluminoxanes (see, for example, Patent Documents 2 and 3) and those using ion-exchangeable layered silicates (for example, Patent Document 4) And 5) are disclosed.

In addition, in order to remove impurities and increase the polymerization efficiency, a number of means for improving the raw material system have recently been proposed, and in order to purify the solvent when the solvent after the polymerization reaction is reused, for example, it is necessary to reuse the solvent. A method of contacting a solvent to be contacted with an adsorbent to adsorb and remove a component derived from a metallocene compound (see Patent Document 6) is disclosed. In order to remove impurities from the catalyst component, a method of purifying a metallocene compound containing an ether compound as an impurity by washing with a halogenated hydrocarbon solvent (see Patent Document 7), a transition metal / aromatic containing impurities Method for fractionating and purifying a system compound by liquid chromatography packed with porous carbon (see Patent Document 8). In order to improve the quality of a metallocene catalyst, inorganic impurities such as metal halides are separated using an organic solvent, A method for removing organic impurities with a particulate adsorbent substance (see Patent Document 9) and the like are disclosed. In order to purify a raw material gas to be reused, an unreacted gas after a polymerization reaction is passed through a fixed-bed adsorption tower. There is also disclosed a method for preventing a decrease in the activity of a metallocene catalyst by removing impurities (see Patent Document 10).
Further, although there is no specific example of impurities in order to remove impurities and increase polymerization efficiency, use of an organoaluminum compound as a remover (scavenger) for removing impurities is also disclosed (for example, See Patent Documents 11 and 12). As the organic aluminum as a remover which is a catalyst detoxifier, triethylaluminum, triisobutylaluminum and the like are mainly used. In this case, conventionally, it was thought that there was no catalyst poison that could not be scavenged by the organic aluminum. However, as will be described later, the present inventors have conducted detailed investigations and have unexpectedly found that a halogen-containing compound becomes a large catalyst poison for a metallocene catalyst.
In any of the above methods, impurities do not seem to be sufficiently detoxified or removed, and the catalyst activity and polymerization efficiency are not sufficiently complete. Further, no method has been realized in which a catalyst poison of a metallocene catalyst is specified and an effective means is employed for the specified substance.

  As described above, the metallocene-based catalyst is more sensitive to impurities in the polymerization reaction system than the Ziegler-type catalyst, and therefore, strict control and management of impurities such as monomers and catalysts in raw materials and the polymerization reaction system are required. It has become a bottleneck for large-scale and efficient industrialization of olefin polymerization by metallocene catalysts, and is recognized as a major problem to be solved.

JP-A-6-206924 (Claim 1, Claims 0013, Paragraph 0063) JP-A-3-234709 (Claim 1 of the claims) JP-A-5-247128 (paragraph 0024) JP-A-11-49812 (Claim 1 of the claims) JP-A-11-140112 (Claim 1 of the claims) JP 2001-62202 A (Claim 1 of the Claims) JP-A-7-97388 (Claim 1 of the claims) JP-A-9-47602 (Claim 1 of the claims) Japanese Unexamined Patent Publication No. 11-510545 (Abstract, Claim 1 of the Claims) JP-A-8-3226 (Claim 1 of the claims) JP-A-5-140227 (paragraph 0061) JP-A-11-60623 (paragraph 0009)

  In the situation of such a problem in the metallocene catalyst, by appropriately controlling impurities such as monomers, catalysts or solvents and impurities in the polymerization reaction system, the catalyst activity and polymerization efficiency are enhanced, and the performance of the metallocene catalyst is sufficiently exhibited. It is considered to be a new important task to maintain a stable polymerization reaction and thereby realize large-scale and efficient industrialization of olefin polymerization using a metallocene catalyst.

It is understood that such a problem is important in the polymerization of olefins using a metallocene catalyst, but in the past, mainly attention was focused on the removal of unspecified impurities in individual raw materials such as a catalyst and a solvent. It has been hardly known to grasp both the raw material system and the polymerization reaction system to perform comprehensive and accurate control of impurities.
The present invention solves this new problem by fully exhibiting the performance of a metallocene catalyst and maintaining a stable polymerization reaction, thereby realizing large-scale and efficient industrialization of olefin polymerization using a metallocene catalyst. It is aimed at. That is, an object of the present invention is to provide a method for producing a polyolefin, which can sufficiently exhibit the performance of a catalyst system and maintain stable production under conditions not affected by catalyst poisons of impurities.

  In the process of studying to effectively increase the catalytic activity and polymerization efficiency in olefin polymerization using a single-site catalyst, particularly its metallocene catalyst, the present inventors have developed conventional techniques for removing impurities from individual raw materials such as catalysts and solvents. Based on this, if both the raw material system and the polymerization reaction system are grasped and comprehensive and accurate control of impurities is performed, catalytic activity and polymerization efficiency can be effectively increased, and thereby the performance of the metallocene catalyst can be sufficiently improved. To solve the above-mentioned problems as a result of comprehensively examining the effects of impurities in the raw material system and the polymerization reaction system. The present invention has been embodied.

In other words, in the polymerization of olefins using a typical metallocene catalyst as a single-site catalyst, the effects of impurities in the raw material system and the polymerization reaction system were comprehensively and experimentally examined, and the results of analysis and analysis of the impurity components were repeated. The present inventors have found and confirmed that a halogen compound is present as an impurity in the raw material system and the polymerization reaction system, which causes a decrease in the catalytic activity of the metallocene catalyst and a deterioration in the polymerization efficiency of olefin polymerization.
Surprisingly, it has been found that the halogen contained in the metallocene complex of the metallocene catalyst itself does not cause such an adverse effect, but rather acts to enhance the catalytic activity and the polymerization efficiency. However, conventionally, a halogen-containing compound may have a good effect on a polymerization system, and Patent Document 4 (paragraph 0051) or Patent Document 5 (paragraphs 0005 to 0006) discloses that a polymerization containing a halogen-containing compound is not effective. There is a description that the activity is improved by performing. However, this action of the halogen-containing compound is considered to be exceptional only when used under the condition of being used in combination with a special ion-exchangeable layered compound.
In the polymerization of olefins with metallocene catalysts, comprehensive and accurate control of halogen impurities in both the raw material system and the polymerization reaction system, i.e., compounds containing halogen, simple halogens, etc. can improve the catalytic activity and polymerization efficiency. The present invention, which can be further improved, has been completed.

Halogen impurities include those derived from raw materials such as solvents and monomers, those produced as by-products during the polymerization reaction, those brought as dirt from the polymerization apparatus, and the like, inorganic halogen compounds, organic halogen compounds, or halogen alone. Or exist as ions or the like (these are sometimes collectively referred to simply as “halogen-containing compounds” hereinafter). Its abundance also depends on the impurity of the raw materials, the conditions of the polymerization reaction and the like.
In addition, in the conventional literature (the upper right column on page 3 of JP-A-3-31304), there is a description of removal of an organic chlorine compound when a polymerization solvent in polymerization using a Ziegler-Natta catalyst is purified for reuse. However, this is not the prior art of the present invention since it merely describes removal from the solvent together with other impurities, but does not describe the amount thereof and does not describe any control in the polymerization reaction.

In the polymerization of olefins with a metallocene catalyst, the present inventors conducted detailed and experimental studies on conditions that effectively increase catalyst activity and polymerization efficiency by comprehensively and precisely controlling halogen-containing compounds as halogen impurities. In order to effectively increase the catalytic activity and polymerization efficiency, the amount of halogen is deeply involved, and it is estimated that the amount is closely related to the amount of the central metal of the metallocene catalyst introduced into the polymerization reaction. Experiments have led to the specific definition of the amount of halogen, and the central structure of the present invention has been formed.
In other words, the present inventors exclude the halogen atoms derived from the catalyst and suppress the contamination of halogen atoms derived from the halogen-containing compound present in the polymerization reaction tank as much as possible. The present inventors have found that by setting the halogen atom to a specific amount or less with respect to the central metal of the metallocene complex to be used, the performance of the catalyst system can be sufficiently exhibited and stable production can be maintained, and the present invention has been completed.
Here, the halogen atom derived from the catalyst means not only the one derived from the metallocene complex but also the one derived from the metallocene complex, even if the cocatalyst or the catalyst carrier contains halogen, as described in detail in paragraph 0031. , And those halogens are also excluded from the control. Further, regarding the organoaluminum in the third component of the catalyst, it is not sufficiently known whether or not the halogen contained therein has an adverse effect on the olefin polymerization. In the polymerization, organoaluminum containing halogen (organoaluminum halide) is not used as the third component of the catalyst.
The essence of the present invention is that the halogen compound accompanying the polymerization raw material, the halogen impurity mixed when the polymerization solvent is reused in a commercial-scale production plant, or the material for maintaining the polymerization apparatus is used. It has been found that mixed organic halides and the like adversely affect the polymerization by the metallocene catalyst, and from such a viewpoint, it can be said that an attempt to increase the activity and polymerization efficiency of the catalyst is a breakthrough. (Such a halogen may be expressed as 'bad halogen'.)
In other words, the feature of the present invention is to control the abundance of a halogen-containing compound as a catalyst poison, and the essence is that the abundance exceeds the range specified in the present invention due to, for example, some abnormality. It is to perform an operation method or a preventive method as described below.

In the above, since the outline of the process of creation and the features of the configuration of the present invention have been outlined, an overview of the present invention will be made here. One invention is defined as a basic invention unit, and the second and subsequent inventions embody or embody the basic invention. (Note that the first to tenth inventions are collectively referred to as "the present invention.")
First invention: In producing a polyolefin by polymerizing an olefin using a single-site catalyst, the gram atomic weight of a halogen atom derived from a halogen-containing compound mixed into a polymerization reaction other than a halogen atom derived from a catalyst component is determined by: A method for improving polyolefin production, comprising controlling the amount of a halogen-containing compound to be 0.8 or less based on the gram atomic weight of a transition metal of a single-site catalyst to be introduced.

Second invention: The method for improving polyolefin production according to the first invention, wherein the single-site catalyst is a metallocene catalyst comprising the following components (A) and (B) and, if necessary, (C).
Component (A): Metallocene complex Component (B): Promoter Component (C): Organoaluminum compound (excluding organoaluminum halide compound)

  Third invention: The method for improving the production of a polyolefin according to the first invention or the second invention, wherein an α-olefin having 3 or more carbon atoms is polymerized or copolymerized as the olefin.

  Fourth invention: The polyolefin of the second invention, wherein the transition metal complex component of the metallocene complex in the metallocene catalyst is a transition metal compound belonging to Groups 4 to 6 of the periodic table having a conjugated five-membered ring ligand. How to improve manufacturing.

  Fifth invention: The co-catalyst for activating the metallocene complex in the metallocene catalyst is any one of an aluminum oxy compound, an ionic compound or a Lewis acid, a solid acid, and an ion-exchangeable layered silicate. An improved method for producing the polyolefin of the second to fourth inventions.

  Sixth invention: The co-catalyst for activating the metallocene complex is an organoboron compound, and the polyolefin to be produced is one that polymerizes ethylene or propylene, one that copolymerizes ethylene with an α-olefin having 3 or more carbon atoms, or propylene. The method for producing a polyolefin according to any one of the second to fifth aspects of the present invention, which comprises copolymerizing another α-olefin having 2 or more carbon atoms.

  Seventh invention: The amount of the organic compound to which the halogen atom is bonded, the amount of the silicon-containing compound to which the halogen atom is bonded, the amount of the aluminum atom-containing compound to which the halogen atom is mixed, and The production of polyolefins according to the first to sixth inventions, characterized in that any or all of the amount of the compound in which the halogen atom is bonded and the amount of the halogen-containing compound which is an impurity from the polymerization apparatus are controlled. How to improve.

  Eighth invention: The method for improving polyolefin production according to the seventh invention, wherein the halogen-containing compound as an impurity from the polymerization apparatus is derived from a gasket sealing agent for the flange.

  Ninth invention: The method for improving polyolefin production according to the first to eighth inventions, wherein the halogen is chlorine.

  Tenth invention: When the gram atomic weight of a halogen atom derived from a halogen-containing compound mixed into the polymerization reaction other than the halogen atom derived from the catalyst component exceeds 0.8 with respect to the gram atomic weight of the transition metal, A method for improving the production of polyolefins according to the first to ninth aspects of the present invention, wherein the amount of halogen-containing compound present in the polymerization reaction is reduced so as to maintain 0.8 or less.

In the present invention, the activity and polymerization efficiency of a single-site catalyst can be greatly enhanced by employing innovative means by controlling halogen compounds in a commercial-scale production plant for olefin polymerization using a single-site catalyst, A remarkable effect is exhibited in that a high-molecular-weight olefin polymer having excellent moldability can be efficiently produced.
Thereby, the performance of the metallocene catalyst can be sufficiently exhibited, a stable polymerization reaction can be maintained, and large-scale and efficient industrialization of olefin polymerization using a metallocene catalyst can be realized.

Hereinafter, embodiments of the present invention will be specifically described in detail focusing on control of a halogen-containing compound in olefin polymerization.
(1) Control of Halogen-Containing Compound (A) Regulation by Gram Atomic Weight As described above, in the present invention, when a olefin is polymerized using a single-site catalyst to produce a polyolefin, other than a halogen atom derived from a catalyst component. The gram atomic weight of the halogen atom derived from the halogen-containing compound mixed in the polymerization reaction is 0.8 or less with respect to the gram atomic weight of the transition metal of the single-site catalyst to be mixed. It is based on a method for improving the production of polyolefins, characterized by controlling the amount. By adopting such a structure, the performance of the catalyst system can be sufficiently exhibited and stable production can be maintained.
Hereinafter, a metallocene catalyst which is a typical example of a single-site catalyst will be specifically described.

  In metallocene-catalyzed olefin polymerization, comprehensive and accurate control of halogens, especially chlorine, bromine and iodine containing poisons, is conducted to test the conditions to effectively increase catalyst activity and polymerization efficiency. In order to effectively increase the catalyst activity and polymerization efficiency by examining the details in detail, the amount of halogen other than the halogen atom derived from the catalyst component must be adjusted to the amount of the central metal of the metallocene catalyst introduced into the polymerization reaction. Knowing that they are closely related, they came to specify the amount of halogen specifically by experiments, and derived from halogen-containing compounds mixed in the polymerization reaction other than halogen atoms derived from the catalyst component. The halogen is adjusted so that the gram atomic weight of the halogen atom is 0.8 or less based on the gram atomic weight of the transition metal of the single-site catalyst to be introduced. It is sufficient to control the amount of mixed-containing compound has been found. This is confirmed by a comparative study of the example and the comparative example described later.

The mixing amount of the halogen-containing compound is controlled so that the gram atomic weight of the halogen atom is preferably 0.6 or less, more preferably 0.3 or less with respect to the gram atomic weight of the transition metal of the single-site catalyst to be introduced. It is preferable that the numerical value is as small as possible, but it is not necessary to make the numerical value much smaller than 0.6 in consideration of the processing difficulty and economical efficiency.
In addition, for example, in the case of 1 mol of dichloroethane, since it has two Cl atoms, it becomes 2 gram atomic weight in terms of halogen.

(B) Prevention of Halogen-Containing Compounds If comprehensive and accurate control of halogen impurities, that is, halogen-containing compounds, in both the raw material system and the polymerization reaction system is performed, catalytic activity and polymerization efficiency can be effectively increased. It is important to prevent the halogen-containing compound from being mixed into the polymerization reactor as much as possible.
As described above, the halogen-containing compound exists as an inorganic halogen compound, an organic halogen compound, a halogen simple substance or an ion, and these are derived from a raw material such as a solvent or a monomer, and have a side reaction during a polymerization reaction. It is produced as a product, and is brought as fouling from a polymerization apparatus.In order to reduce them as much as possible, materials such as solvents and monomers are sufficiently purified in advance, side reactions in the polymerization reaction are controlled, and the polymerization apparatus is controlled. It is necessary to take measures to prevent the occurrence of dirt from the surface.

As a specific method for controlling the amount of the halogen-containing compound,
a. Inspection when accepting raw materials and auxiliaries Analyze the amount of halogen and use the method if it is less than the preset allowable amount.
b. Purification of Raw Materials and Aids As a method for purifying the raw materials, a usual method is used, and for example, a method by distillation or a chemical reaction, or a physical method such as adsorption can be used.
As a specific purification method, a method in which a raw material or a solvent is passed through a purification tower filled with an adsorbent that chemically or physically adsorbs a halogen-containing compound can be exemplified. It is necessary to select an appropriate adsorbent according to the purpose. An adsorbent capable of adsorbing a halogen-containing compound is disclosed in "Catalyst Notebook" issued by Sued Chemie Catalysts, Inc. For example, ZnO, CaO, CuO, Al ₂ O ₃ , Na ₂ O and the like.
As another specific purification method, a method of removing a halogen-containing compound by precision distillation of a raw material or a solvent can be exemplified.
c. Removal of Halogen-Containing Compound in Polymerization Reaction System According to the above-described method, it is possible to prevent the halogen-containing compound from being mixed in from a raw material or an auxiliary to some extent. However, a gasket sealant used for equipment maintenance sometimes contains a halogen-containing compound, and it has been confirmed that the halogen-containing compound is mixed into the system from the sealing portion of the flange. Such impurities are so-called "generated" in the system, and require a removing means in the reaction system. Specifically, b. The use of adsorbents mentioned in can be employed.
d. Others This is due to the control of side reactions in the polymerization reaction. The conditions such as temperature and pressure are examined to limit the amount of halogen by-products. It is also important to control the amount of halogen by monitoring the amount of halogen while monitoring the polymerization reaction.
A sealant containing as little halogen as possible is used in the polymerization apparatus, and the inside of the apparatus is kept clean in advance.

As described above, the halogen contained in the metallocene complex of the metallocene catalyst does not cause such an adverse effect, but rather acts to enhance the catalytic activity and the polymerization efficiency. In addition, some co-catalysts such as boron compounds, or some carriers that support the catalyst, contain halogen as a component thereof, but the co-catalyst or the carrier is used after its effectiveness is evaluated. Therefore, even those containing halogen can be used, and in the present invention, the halogen supplied by such a component is excluded from the control. However, it is preferable that the halogen-containing compound as an impurity accompanying each catalyst component is purified and removed in advance.
In the present invention, it is one of the features of the present invention that the halogen derived from the catalyst material does not need to be controlled, and the value of the halogen amount can be calculated in advance at the time of polymerization and is subtracted from the control of the halogen amount.
By the way, those containing fluorine may give good results for the polymerization system. In this sense, it can be understood that the present invention is a technique for sufficiently exerting its function in a selected reaction system.
In the present invention, the halogen that becomes a catalyst poison includes fluorine, chlorine, bromine, and iodine.However, since halogen accompanying a polymer material is generally chlorine, a chlorine atom is generally assumed as the halogen. You.

(C) Principal Sources of Halogen-Containing Compounds The following compounds are exemplified as the source of a halogen-containing compound that is a catalyst poison that reduces the polymerization activity of a metallocene catalyst.
a. The main route of mixing the inorganic halogen compound with the Al atom-containing compound is as follows: the solvent used in the Ziegler-Natta catalyst is mixed as a raw material Al atom-containing compound component and mixed as an organic aluminum impurity to form a metallocene polymerization. In which the solvent is diverted.
By the way, in the production process of such an organoaluminum, a method utilizing a disproportionation reaction between a trialkylaluminum or an alkylaluminum halide and aluminum trichloride is generally used as a method for producing an alkylaluminum halide. .
In the production of such an aluminum alkyl halide, after the production of the aluminum halide or the aluminum alkyl halide, the reaction tank, the used raw material tank or the stagnant portions of the pipes and the like are not sufficiently washed and the trialkyl aluminum halide is used. When an organic aluminum containing no halogen is produced, a residual halogen-containing compound may be mixed into a product.
In the case of organoaluminum, it is extremely difficult to remove a halogen component such as chlorine contained as an impurity by refining. Therefore, it is important that the halogen component is not mixed in the production stage and when used in the production of polyolefin.

b. Organic Halogen Compounds Organic halogen compounds are often mixed in organic solvents used for catalyst production and dilution. In particular, during the production of the catalyst, if the solvent used in producing the Ziegler-Natta catalyst is recovered and reused, the solvent such as chlorine atoms contained in titanium trichloride or titanium tetrachloride may react. When it occurs, it is generated and may be mixed as it is.
Further, it may be contained in a sealant component used in a gasket of a reaction tank or a pipe in a polymerization reaction, and this also causes mixing.
Examples of specific compounds include dichloromethane, chloroform, chloroethane, dichloroethane, trichloroethane, tetrachloroethane, chloropropane, dichloropropane, trichloropropane, chlorobutane, dichlorobutane, chloropentane, dichloropentane, chlorohexane, dichlorohexane, chloroheptane, Aliphatic compounds such as dichloroheptane and polychlorotrifluoroethane are exemplified.
As the organic halogen compound, an aromatic compound or a compound containing a hetero atom may be mixed.

c. As a silicon atom-containing halogen compound A silicon atom-containing halogen compound is used as a by-product when an electron donor (so-called silicon donor) for imparting stereoregularity is added, for example, in the case of producing a Ziegler-Natta catalyst. May be included in cleaning and recovery solvents. When this solvent is used after re-purification, it is considered that a halogen compound containing a silicon atom is mixed.
Examples of specific compounds include chlorotrimethylsilane, dichlorodimethylsilane, methyltrichlorosilane, ethyltrichlorosilane, butyltrichlorosilane, cyclopentyltrichlorosilane, phenyltrichlorosilane, chlorocyclohexyldimethylsilane, trichlorocyclohexylsilane, dichloromethylvinylsilane, and the like. Is mentioned. In addition, it is also conceivable to mix a silicon atom-containing compound further containing an aromatic group or a hetero atom.

(D) Consideration of Inhibition of Polymerization Reaction by Halogen-Containing Compound The halogen-containing compound can be considered to inhibit normal olefin polymerization by coordinating with the transition metal compound and altering the active site.
In general, the use of organoaluminum is known to have an effect of suppressing the active site from being altered by a polar compound, but the halogen-containing compound is a scavenger despite being a polar compound. Shows a specific behavior in which the transformation of the active site by the organic aluminum cannot be suppressed.
It is considered that the reason for this is that the Lewis basicity of the halogen atom, that is, the property of easily interacting with the cationic species is not lost even by the inhibitory action of the organoaluminum.

(E) Halogen atom analysis method As an analysis method of a halogen compound used for controlling the amount of halogen present in the polymerization reaction system, an atomic absorption method, a gas chromatograph, a liquid chromatograph or an ion chromatograph was used. The method can be exemplified.
In addition, in addition to the above-mentioned method, the method of analyzing a chlorine compound is to preliminarily precipitate silver chloride with an excess of silver nitrate, and then determine the excess silver nitrate by titration or absorbance measurement with an ammonium thiocyanate solution using a ferric ammonium sulfate indicator. An analysis method or the like is used.

Hereinafter, a method for assaying the halogen (chlorine) atomic weight present in the reactor during the polymerization reaction will be described as an example.
a. A method in which the amount of chlorine atoms contained in the raw materials is measured in advance, and the amount of chlorine atoms present in the reactor is detected based on the amount of each raw material introduced into the reactor. B. After introducing each raw material into the reactor, or in the case of a continuous process, after the production conditions have reached a steady state, a method of directly sampling from the reactor to test the chlorine atom abundance c. Sampling is performed in the middle of the line that circulates each raw material to determine the amount of chlorine atoms.Based on the balance between the amount circulated in the reaction system and each raw material discharged outside the reaction system, the amount of chlorine atoms introduced into the reactor is determined. A test method is used.

(2) Single Site Catalyst and Metallocene Catalyst The present invention basically relates to a single site catalyst, and details a metallocene catalyst, which is a typical example thereof, as an example.
The metallocene catalyst used in the present invention can be used without any particular limitation as long as it is known. The metallocene catalyst is generally (A) a metallocene complex comprising a transition metal compound such as Group 4 of the Periodic Table having a conjugated five-membered ring ligand, (B) a cocatalyst for activating the metallocene complex, and if necessary, It is composed of the (C) organoaluminum compound used. Depending on the characteristics of the olefin polymerization process, it is necessary to form particles, so that the carrier may further comprise (D) a carrier.
(In the description of the present specification, a short-periodic table is used as a periodic table of elements.)

(A) Metallocene Complex A typical example of the metallocene complex used in the present invention is a metallocene complex of a transition metal compound belonging to Groups 4 to 6 of the periodic table having a conjugated five-membered ring ligand. Among them, those represented by any of the following general formulas are preferable.

In the formula, A and A ′ are a cyclopentadienyl group which may have a substituent. An example of the substituent is a hydrocarbon group having 1 to 30 carbon atoms. Even if this hydrocarbon group is bonded to the cyclopentadienyl group as a monovalent group, when there are a plurality of these, two of them are bonded at the other end (ω-end) to form cyclopentadienyl. It may form a ring with a part of the enyl. Other examples include an indenyl group, a fluorenyl group, and an azulenyl group. These groups may further have a substituent on the sub-ring. Preferred among these are an indenyl group and an azulenyl group.
Q represents a bonding group that bridges between two conjugated five-membered ring ligands at an arbitrary position, and specifically, is preferably an alkylene group, a silylene group, or a germylene group.
These groups may further have a substituent.
M is a metal atom of a transition metal selected from Groups 4 to 6 of the periodic table, preferably, titanium, zirconium, hafnium or the like. In particular, zirconium and hafnium are preferred.
X and Y are auxiliary ligands, which react with the component (B) to form an active metallocene having olefin polymerization ability. Therefore, as long as this object is achieved, X and Y are not limited by the type of ligand, and each of X and Y may be a hydrogen atom, a halogen atom, a hydrocarbon group, or a hydrocarbon group optionally having a hetero atom. Can be exemplified. Of these, a hydrocarbon group having 1 to 10 carbon atoms or a halogen atom is preferable.

(B) Promoter (activator component)
The cocatalyst is a component that activates the metallocene complex and is a compound that can react with an auxiliary ligand of the metallocene complex to convert the complex into an active species having olefin polymerization ability. -1) to (B-4).
(B-1) Aluminum oxy compound (B-2) Ionic compound or Lewis acid capable of reacting with component (A) to convert component (A) into a cation (B-3) Solid acid (B- 4) Ion-exchange layered silicate

  It is well known that (B-1) an aluminum oxy compound can activate a metallocene complex, and specific examples of such a compound include compounds represented by the following general formulas. .

In the above formulas, R ¹ represents a hydrogen atom or a hydrocarbon residue, preferably a hydrocarbon residue having 1 to 10 carbon atoms, particularly preferably a hydrocarbon residue having 1 to 6 carbon atoms. Further, a plurality of R ¹ may be the same or different. P represents an integer of 0 to 40, preferably 2 to 30.
Of the general formulas, the compounds represented by the first and second formulas are compounds also referred to as aluminoxanes, and among these, methylaluminoxane or methylisobutylaluminoxane is preferable. The above aluminoxane can be used in combination of two or more kinds in each group and between groups. The aluminoxane can be prepared under various known conditions.
The compound represented by the third general formula is a 10: 1 to 1 type of trialkylaluminum or two or more trialkylaluminums and an alkylboronic acid represented by the general formula R ² B (OH) ₂ . It can be obtained by a 1: 1 (molar ratio) reaction. In the general formula, R ¹ and R ² represent a hydrocarbon residue having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms.

The compound (B-2) is an ionic compound or a Lewis acidic compound capable of reacting with the component (A) to convert the component (A) into a cation. Cations such as ammonium cations and ammonium cations and anions such as tetraphenyl borate, tetrakis (3,5-difluorophenyl) borate, tetrakis (pentafluorophenyl) borate and tetrakis (pentafluorophenyl) aluminate form an ion pair. Compounds that are forming are mentioned.
Examples of the above-mentioned Lewis acidic compound include various organic boron compounds, for example, tris (pentafluorophenyl) boron. Alternatively, metal halide compounds such as aluminum chloride and magnesium chloride are exemplified.
Some of the above-mentioned Lewis acidic compounds can be regarded as ionic compounds capable of reacting with the component (A) to convert the component (A) into a cation. Metallocene catalysts using the above-mentioned non-coordinating boron compounds are exemplified in JP-A-3-234709, JP-A-5-247128 and the like.
These ionic compounds or Lewis acidic compounds are preferably organic boron compounds. The term "organic boron compound" used herein also includes an ionic compound in which an organic boron compound exists as a part of an ion pair.

Specific examples of the organic boron compound include at least one compound represented by the following general formula (1) which is a Lewis acidic compound and the following general formula (2) which is an ionic compound.
BR ³ R ⁴ R ⁵ Formula (1)
(In the formula, R ^{3 to} R ⁵ may be the same or different, and represent a hydrocarbon containing a halogenated aryl group or halogenated aryloxy group having 1 to 14 carbon atoms.)
A (BR ⁶ R ⁷ R ⁸ R ⁹ ) _n Formula (2)
(Wherein A is a quaternary amine or quaternary ammonium salt or a carbocation or a metal cation having a valence of +1 to +4, and R ^{6 to} R ⁹ may be the same or different, respectively, and may have 1 to 14 carbon atoms. A hydrocarbon group containing a halogenated aryl group or a halogenated alkyl group, and n represents an integer of 1 to 4.)

Specific examples of the hydrocarbon groups of the general formulas (1) and (2) are preferably a pentafluorophenyl group, a pentafluorobenzyl group, a tetrafluorophenyl group, and a tetrafluorotolyl group.
Further, specific examples of A in the general formula (2) are preferably N, N-dimethylanilinium and triphenylmethyl.

  Examples of the solid acid of (B-3) include alumina, silica-alumina, silica-magnesia, and the like.

The ion-exchangeable layered compound (B-4) occupies most of the clay mineral, and is preferably an ion-exchanged layered silicate.
The ion-exchange layered silicate (hereinafter sometimes simply referred to as “silicate”) has a crystal structure in which planes formed by ionic bonds and the like are stacked in parallel with each other by a bonding force and contained. Refers to a silicate compound whose ions are exchangeable. Most silicates are naturally produced mainly as a main component of clay minerals, so they often contain impurities (quartz, cristobalite, etc.) other than ion-exchangeable layered silicates. You may go out. Various known silicates can be used. Specific examples include the following layered silicates described by Haruo Shimizu, "Clay Mineralogy", Asakura Shoten (1995).
2: 1 type minerals Smectites such as montmorillonite, zauconite, beidellite, nontronite, saponite, hectorite, stevensite; vermiculites such as vermiculite;
Pyrophyllite-talc such as pyrophyllite and talc; chlorite such as Mg chlorite;
2: 1 ribbon type minerals Sepiolite, Palygorskite, etc.

The silicate used as a raw material in the present invention may be a layered silicate formed with the above-mentioned mixed layer. In the present invention, the silicate as a main component is preferably a silicate having a 2: 1 type structure, more preferably a smectite group, and particularly preferably montmorillonite. The silicate used in the present invention, which is obtained as a natural product or an industrial raw material, can be used without any particular treatment, but is preferably subjected to a chemical treatment. Specific examples include acid treatment, alkali treatment, salt treatment, and organic substance treatment. These processes may be used in combination with each other. In the present invention, these treatment conditions are not particularly limited, and known conditions can be used.
In addition, since these ion-exchangeable layered silicates usually contain adsorbed water and interlayer water, it is preferable to use the ion-exchanged layered silicate after removing water by, for example, heating and dehydrating under an inert gas flow.

(C) Organoaluminum Compound In the present invention, a halogen-free organoaluminum compound is used as the metallocene catalyst system as required. Preferably,
General formula AlR _3-i X _i
(Wherein, R represents a hydrocarbon group having 1 to 20 carbon atoms, X represents hydrogen, an alkoxy group, a phenoxy group, a siloxy group or an amino group, and i represents a number satisfying 0 ≦ i <3, provided that X represents hydrogen. In this case, the compound represented by i is 0 <i <3.) Is used. Further, among the component (B) promoters, the compounds exemplified as the (B-1) aluminum oxy compound can also be used.

Specifically, trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trioctylaluminum, or dimethylaluminum methoxide, diethylaluminum methoxide, diisobutylaluminum methoxide, diisobutylaluminum ethoxide, etc. Alkoxy group-containing alkyl aluminum, or phenoxy group-containing aluminum such as dimethyl aluminum phenoxide, or siloxy group-containing aluminum such as dimethyl aluminum trimethylsiloxide or dimethyl aluminum triphenylsiloxide, or (diethylamino) diethylaluminum, di (diethylamino) ethyl Amino group-containing alkyl aluminum such as aluminum, or A halide-containing alkyl aluminum such as ethyl aluminum halide.
Of these, trialkyl aluminum is particularly preferred. More preferred are triisobutylaluminum and trioctylaluminum.

(D) Amount of catalyst component used and others a. Use amount The use amounts of the component (A) and the component (B) are used in an optimum ratio in each combination.
When the component (B) is an aluminum oxy compound, the molar ratio of Al / transition metal is usually from 10 to 100,000, preferably from 100 to 20,000, particularly from 100 to 10,000. On the other hand, when an ionic compound or Lewis acid is used as the component (B), the molar ratio of the transition metal to the transition metal is in the range of 0.1 to 1000, preferably 0.5 to 100, and more preferably 1 to 50. .
When a solid acid or an ion-exchange layered silicate is used as the component (B), the transition metal complex is used in an amount of 0.001 to 10 mmol, preferably 0.001 to 1 mmol, per 1 g of the component (B).
These usage ratios show typical ratio examples, and the present invention is limited by the range of the usage ratio described above if the catalyst is in accordance with its purpose. It is natural that they must not.

b. Prepolymerization treatment
Before using a catalyst for polyolefin production comprising a transition metal complex and a cocatalyst as a catalyst for olefin polymerization (main polymerization), the catalyst is supported on a carrier, if necessary, and then ethylene, propylene, 1-butene, 1-hexene is used. , 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane, styrene and the like may be preliminarily polymerized in a small amount. A known method can be used for the prepolymerization method.

(3) Olefin used for polymerization and polymerization reaction Examples of the olefin that can be polymerized by the olefin polymerization catalyst of the present invention include ethylene, propylene, butene-1, 3-methyl-1-butene, 3-methyl-1-pentene, Examples include conjugated dienes such as 4-methyl-1-pentene, vinylcycloalkane and butadiene, non-conjugated dienes such as 1,5-hexadiene, styrene and derivatives thereof. In particular, propylene is preferably used.
The polymerization can be suitably applied to random copolymerization and block copolymerization in addition to homopolymerization. Examples of the comonomer at the time of copolymerization include the above-mentioned olefins, particularly, ethylene.

The polymerization reaction is slurry polymerization and solution polymerization performed in the presence of an inert hydrocarbon solvent such as butane, pentane, hexane, heptane, toluene, and cyclohexane, bulk polymerization performed in the presence of a solvent such as liquefied α-olefin, α-olefin It is preferred to carry out by high-pressure ionic polymerization performed under the critical conditions of the above or by gas-phase polymerization in a state where a liquid phase of a solvent or a monomer does not substantially exist. The gas phase polymerization can be performed using a reaction apparatus such as a fluidized bed, a stirred bed, and a stirred fluidized bed equipped with a stirring mixer.
The conditions such as the polymerization temperature and the polymerization pressure are not particularly limited, but the polymerization temperature is generally -50 to 350 ° C, preferably 0 to 300 ° C, and the polymerization pressure is usually normal pressure to about 2000 kgf / cm ² , It is preferably in the range of normal pressure to 1500 kgf / cm ² , more preferably in the range of normal pressure to 1300 kgf / cm ² . Further, hydrogen may be present as a molecular weight regulator in the polymerization system.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following examples.
The handling of the catalyst components was all performed under a nitrogen atmosphere. Unless otherwise specified, hexane used as a solvent in the examples refers to a reagent-grade hexane passed through a column packed with molecular sieve (MS) to remove water, and heptane also refers to a reagent-grade heptane Indicates that water was removed through a column packed with MS.

[Halogen atom analysis]
1. Collection and Analysis of Halogen Atom-Containing Compound in Gas Here, the halogen atom means each atom of fluorine, chlorine, bromine and iodine, unless otherwise specified.
Halogen atom-containing compounds in ethylene, propylene, hydrogen and nitrogen were collected by the following method.
70 ml of a NaOH water / ethanol solution (0.1 mol / L, the volume ratio of water and ethanol was 1/49) was added to each of the two absorption tubes, which were connected in series to cool the absorption tubes.
The halogen atom-containing compound was absorbed while 30 to 60 L of the gas to be measured was passed through the absorption tube at about 0.5 to 1.0 L / min. Next, 30 ml of the NaOH solution in each absorption tube was separated and neutralized with an aqueous nitric acid solution. This was analyzed by ion chromatography.
Equipment: DIONEX DX-500
Column: AG11 + AS11
Constant temperature: 35 ° C
Eluent flow rate: 2 ml / min Eluent: NaOH aqueous solution (0.1 mmol / L)
Detector: based on electrical conductivity As a result, no halogen atom-containing compound was detected in any of the raw materials.

2. Collection and Analysis of Halogen-Containing Compound in Solvent Halogen-containing compounds in hexane, heptane and toluene were collected by the following method.
40 ml of an aqueous NaOH solution (20 wt%) was taken out into a separating funnel together with 200 ml of hexane, heptane and toluene to be measured, set on a shaker and shaken for 1 hour. Thereafter, 15 ml of an aqueous NaOH solution was collected and neutralized with an aqueous nitric acid solution, and analyzed by ion chromatography under the above-described measurement conditions.
As a result, no halogen atom was detected in the special grade hexane, the special grade heptane and the special grade toluene.

3-1. Collection and analysis of compounds containing chlorine, bromine or iodine atoms in diluents of organoaluminum Chlorine, bromine and iodine atoms have similar chemical properties. Therefore, in the following detection method utilizing the color reaction of iron thiocyanate, each of these atoms is detected simultaneously, and the abundance is indicated by integrating it with the absorbance at a wavelength of 460 nm.
A heptane diluent was fractionated into a separating funnel so as to be equivalent to 0.5 g of the organoaluminum compound to be analyzed, and the total amount of the solution was adjusted to 200 ml. To this, 40 ml of an aqueous solution of NaOH (20 wt%) was added, and the mixture was set on a shaker and shaken for 1 hour. Thereafter, 15 ml was taken from the NaOH aqueous solution phase and neutralized with a nitric acid aqueous solution. To the neutralized sample was added 10 ml of a ferric ammonium sulfate solution (ammonium ferric sulfate, 60 g dissolved in 6N nitric acid). Next, 5 ml of a mercuric thiocyanate solution (3.0 g of mercuric thiocyanate dissolved in 1 L of ethanol (95 vol%)) was added, and the total volume was adjusted to 50 ml with water, followed by shaking and coloring. Ten minutes after color development, the absorbance at 460 nm was measured (Hitachi spectrophotometer: U-3200).
The chlorine, bromine and iodine atoms in the measurement sample were quantified by comparing a blank measurement separately performed with a calibration curve prepared using a sample having a known content of chlorine, bromine and iodine atoms. As a result, chlorine, bromine and iodine atoms were not detected in the organoaluminum compound used this time.

3-2. Collection and analysis of fluorine atom-containing compounds in organic aluminum dilutions Heptane-diluted solution was collected in a separating funnel for collecting the fluorine atom-containing compound so as to be 0.5 g as the organoaluminum compound to be analyzed, and the total amount of the solution was adjusted to 200 ml. To this was added 40 ml of an aqueous NaOH solution (20 wt%), and the mixture was set on a shaker and shaken for 1 hour. Thereafter, 15 ml was taken from the NaOH aqueous solution phase and neutralized with a nitric acid aqueous solution.
2. Zr- the 0.1g of p- dimethylamino azo phenylarsonic acid and zirconium oxychloride Preparation 0.1g of acid suspension of the azo dyes (ZrOCl ₂ · _{8H 2} O) separately added to hydrochloric acid (6 mol / L) Melt. Warm these solutions to 40-60 ° C and slowly add the azo dye solution to the zirconium solution and stir well. After standing for 30 minutes or longer, the insoluble red-brown suspension was centrifuged, washed repeatedly with hydrochloric acid (1 mol / L), suspended in 500 ml of hydrochloric acid (1 mol / L), and stored in a cool dark place.
3. Analysis of fluorine content 10 ml of the solution obtained in the above was placed in a 20 ml stoppered test tube, and 2.0 ml of hydrochloric acid (6 mol / L) and 1.0 ml of an azo dye suspension were added. After stoppering and shaking for several seconds and standing for 15 minutes, the mixture was immediately filtered using a filter paper. The filtrate was placed in another dry stoppered test tube. About 1 ml of carbon tetrachloride was added, stoppered, shaken for a few seconds, and quickly centrifuged for a few minutes. The absorbance of the transparent pink aqueous solution was measured at a wavelength of 500 nm. As a result, no fluorine atom was detected.

[Physical properties of polymer]
Melt flow rate (MFR)
According to the JIS-K7210-1995 test method, polypropylene was measured at 230 ° C under a load of 2.16 kgf, and polyethylene was measured at 190 ° C under a load of 2.16 kgf.

[Olefin Polymerization Example 1: Reference Example 1] Production of Propylene Homopolymer After the inside of an autoclave equipped with a rupturable plate inside a 2.4-liter stirred aerated autoclave was sufficiently replaced with nitrogen, a special grade heptane (Wako Pure Chemical Industries, Ltd.) 1.0 L of a reagent-specified product manufactured by the same company through a MS packed column to remove water) was introduced. The rupture disk is used for bringing a specific catalyst component into contact under a polymerization atmosphere. 3.5 ml of a heptane solution of trinormal octyl aluminum (0.1 mmol-Al / ml heptane; heptane uses the same purified heptane as described above) was added to toluene in an autoclave, followed by triphenylmethyltetrakispentafluorophenyl. 6.8 ml of a toluene solution of borate (0.62 μmol / ml; toluene was manufactured by Wako Pure Chemical Industries, Ltd. and passed through a MS packed column to remove water from a special grade reagent) was added. On the other hand, 2.8 ml of a toluene solution of dimethylsilylenebis (4,5,6,7-tetrahydroindenyl) zirconium dimethyl (1.0 μmol / ml; toluene uses the same purified toluene as above) is provided on the rupture disk side. Was added. Next, the internal pressure of the autoclave was purged. Thereafter, the temperature of the autoclave was raised to 85 ° C., and the rupture disk was broken by propylene pressure. Then, polymerization was performed at 85 ° C. for 1 hour while controlling the partial pressure of propylene in the autoclave to 0.5 MPa. As a result, 29 g of a polymer was obtained. The activity per 1 g of the metallocene complex was 25,000 g polymer. The activity of Example 1 was 111%. When the chlorine atom content in heptane and toluene was measured, it was below the detection limit (<20 ppb). No other halogen atoms (F, Br, I) were detected.

[Example 1] Production of propylene homopolymer In olefin polymerization example 1, heptane to be introduced into a 2.4 L autoclave was recovered and purified heptane used in a polypropylene production plant (using a Ziegler-Natta catalyst). Polymerization was carried out under the same conditions except that heptane A was used. As a result, 26 g of a polymer was obtained. At this time, the activity per 1 g of the metallocene complex was 22,400 g of the polymer.
When the halogen content in the recovered heptane A was measured, Cl was 0.05 wtppm. Assuming that the specific gravity of heptane is 0.67, the total number of moles of Cl atoms in the solvent is 0.94 μmol, and the gram atomic weight ratio of Cl atoms to the complex is 0.34. No other halogen atoms (F, Br, I) were detected.
In Examples 2 to 10 and Comparative Examples 1 to 7 and 9 to 10 described below, other halogens (F, Br, I) were not detected unless otherwise specified.

[Example 2] Production of propylene homopolymer Instead of using recovered heptane A, recovered purified heptane (hereinafter referred to as recovered heptane B) used in a polyethylene production plant (using a Ziegler-Natta catalyst) was used. Except that 0 L was used, the procedure was the same as in Example 1, and as a result, 22 g of a polymer was obtained. The activity per 1 g of the metallocene complex was 19000 g of the polymer. It was 85% of the activity of Example 1. When the halogen content in the recovered heptane B was measured, Cl was 0.10 ppm. The gram atomic weight ratio of Cl atoms to complex metals is 0.69.

[Comparative Example 1] Production of propylene homopolymer Instead of using recovered heptane A, a recovered and purified heptane (hereinafter referred to as recovered heptane C) used in a polypropylene production plant (using a Ziegler-Natta catalyst) was used. Except that 0 L was used, the same procedure as in Example 1 was carried out, and as a result, 16 g of a polymer was obtained. The activity per 1 g of the metallocene complex was 13,800 g of the polymer. The activity of Example 1 was reduced to 62%. When the halogen content in the recovered heptane C was measured, Cl was 0.14 ppm. The gram atomic weight ratio of Cl atoms to complex metals is 0.96.

[Comparative Example 2] Production of Propylene Homopolymer After sufficiently replacing the inside of a 2.4-liter stirred autoclave equipped with a rupture plate inside the autoclave with nitrogen, 1.0 L of special grade heptane was introduced. The rupture disk is used for bringing a specific catalyst component into contact under a polymerization atmosphere. 3.5 ml of a heptane solution of trinormal octyl aluminum (0.1 mmol-Al / ml heptane; heptane uses the same special grade heptane as above) in toluene in an autoclave, and a toluene solution of triphenylmethyltetrakispentafluorophenyl borate 6.8 ml of (0.62 μmol / ml; toluene was manufactured by Wako Pure Chemical Industries, Ltd., a special-grade reagent passed through an MS packed column to remove water), and a toluene solution of aluminum trichloride (1.0 μmol / ml) 0.9 ml of toluene). On the other hand, 2.8 ml of a toluene solution of dimethylsilylenebis (4,5,6,7-tetrahydroindenyl) zirconium dimethyl (1.0 μmol / ml; toluene uses the same purified toluene as above) is provided on the rupture disk side. Was added. Next, the internal pressure of the autoclave was purged. Thereafter, the temperature of the autoclave was raised to 85 ° C., and the rupture disk was broken by propylene pressure. Then, polymerization was performed at 85 ° C. for 1 hour while controlling the partial pressure of propylene in the autoclave to 0.5 MPa. As a result, 12 g of a polymer was obtained. At this time, the activity per 1 g of the metallocene complex was 10,300 g of the polymer. The activity of Example 1 was 46%. The MFR was too high to measure. The gram atomic weight ratio of Cl atoms to the complex is 1.

[Olefin Polymerization Example 2: Reference Example 2] Production of Ethylene Homopolymer The inside of a 2.4-liter stirred autoclave equipped with a rupture plate inside the autoclave was sufficiently replaced with nitrogen, and then used in olefin polymerization example 1. 1 L of special grade heptane was introduced. 3.5 ml of a heptane solution of trinormal octyl aluminum (0.1 mmol-Al / ml heptane; heptane uses the same purified heptane as described above) was added to toluene in an autoclave, followed by triphenylmethyltetrakispentafluorophenyl. 6.8 ml of a toluene solution of borate (0.62 μmol / ml; toluene was manufactured by Wako Pure Chemical Industries, Ltd. and passed through a MS packed column to remove water from a special grade reagent) was added. On the other hand, 2.8 ml of a toluene solution of dimethylsilylenebis (4,5,6,7-tetrahydroindenyl) zirconium dimethyl (1.0 μmol / ml; toluene uses the same purified toluene as above) is provided on the rupture disk side. Was added. Next, the internal pressure of the autoclave was purged, and 65 cc of hydrogen was introduced. Thereafter, the temperature of the autoclave was raised to 85 ° C., and the rupture disk was broken by ethylene pressure. Then, polymerization was carried out at 85 ° C. for 1 hour while controlling the partial pressure of ethylene in the autoclave to be 0.1 MPa. As a result, 81 g of a polymer was obtained. The activity per 1 g of the metallocene complex was 69,800 g of the polymer. The activity of Example 3 was 105%. MFR was 0.2 g / 10 min.

[Example 3] Production of ethylene homopolymer In olefin polymerization Example 2, polymerization was carried out under the same conditions except that 1.0 L of the recovered heptane A used in Example 1 was introduced into a 2.4 L autoclave instead of the special grade heptane. went. As a result, 77 g of a polymer was obtained. At this time, the activity per 1 g of the metallocene complex was 6,640.
It was 0 g polymer. MFR was 0.2 g / 10 min. The halogen content in the recovered heptane A is 0.05 ppm Cl. The gram atomic weight ratio of Cl atom to complex metal is 0.34.

Example 4 Production of Ethylene Homopolymer In the same manner as in Example 3, except that 1.0 L of recovered heptane B was used instead of using recovered heptane A, the result was that 69 g of a polymer was obtained. The activity per 1 g of the metallocene complex was 59,500 g of the polymer. The activity of Example 3 was 90%. MFR was 0.5 g / 10 min. As for the halogen content in the recovered heptane B, Cl is 0.10 ppm. The gram atomic weight ratio of Cl atoms to complex metals is 0.69.

[Comparative Example 3] Production of ethylene homopolymer In Example 3, instead of using recovered heptane A, the same procedure was performed except that 1.0 L of recovered heptane C used in Comparative Example 1 was used. As a result, 55 g of a polymer was obtained. Obtained. The activity per 1 g of the metallocene complex was 47,400 g of the polymer. 71 for the activity of Example 3
%. MFR was 2.0 g / 10 min. The halogen content in the recovered heptane C is 0.14 ppm of Cl. The gram atomic weight ratio of Cl atom to complex metal is 0.9.
It becomes 6.

Comparative Example 4 Production of Ethylene Homopolymer A 2.4-liter stirred autoclave equipped with a rupture plate inside the autoclave was sufficiently purged with nitrogen, and then 1.0 L of special grade heptane was introduced. The rupture disk is used for bringing a specific catalyst component into contact under a polymerization atmosphere. 3.5 ml of a heptane solution of trinormal octyl aluminum (0.1 mmol-Al / ml heptane; heptane uses the same special grade heptane as above) in toluene in an autoclave, and a toluene solution of triphenylmethyltetrakispentafluorophenyl borate 6.8 ml of (0.62 μmol / ml; toluene was manufactured by Wako Pure Chemical Industries, Ltd., a special-grade reagent passed through an MS packed column to remove water), and a toluene solution of aluminum trichloride (1.0 μmol / ml) 0.9 ml of toluene). On the other hand, 2.8 ml of a toluene solution of dimethylsilylenebis (4,5,6,7-tetrahydroindenyl) zirconium dimethyl (1.0 μmol / ml; toluene uses the same purified toluene as above) is provided on the rupture disk side. Was added. Next, the internal pressure of the autoclave was purged, and 65 cc of hydrogen was introduced. Thereafter, the temperature of the autoclave was raised to 85 ° C., and the rupture plate was broken by ethylene pressure. Then, the ethylene pressure in the autoclave was controlled to be 0.1 MPa, and polymerization was performed at 85 ° C. for 1 hour. . As a result, 45 g of a polymer was obtained. At this time, the activity per 1 g of the metallocene complex was 38,800 g of the polymer. The activity for Example 3 was 58%. The MFR is 3.5 g / 10 min, and the gram atomic weight ratio of Cl atom to complex is 1.

[Comparative Example 5] Production of ethylene homopolymer In the polymerization of ethylene in Comparative Example 4, 2.8 ml of a toluene solution of n-butyl chloride (1.0 µmol / ml) was used instead of using a toluene solution of aluminum trichloride. Except performing, it carried out similarly to the comparative example 4. As a result, 53 g of a polymer was obtained. At this time, the activity per 1 g of the metallocene complex was 45,700 g of the polymer. The activity for Example 3 was 69%. The MFR is 2.5 g / 10 min, and the gram atomic weight ratio of Cl atom to complex is 1.

[Olefin polymerization example 3] Catalyst production and preliminary polymerization
The following operations were performed using a solvent and a monomer that had been deoxygenated and dehydrated under an inert gas. When the halogen content in the solvent used was measured, it was not detected.
In a flask having a volume of 200 mL, (r) -dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (2-fluoro-4-biphenylyl) -4H-azulenyl}] hafnium (304 μmol) was added to toluene (304 μmol). 60 mL), and 0.85 mL (600 μmol) of a solution of triisobutylaluminum in heptane was added, followed by stirring at room temperature for 60 minutes. Next, the reaction product was added to a 1 L flask containing 9.9 g (85 mmol-Al) of MAO-supported silica manufactured by Witco and 100 ml of heptane, and the mixture was stirred at room temperature for 60 minutes.
Thereafter, 340 mL of heptane was further added to this slurry and introduced into a 1 L stirred autoclave, and propylene was supplied at 40 ° C. for 120 minutes at a constant rate of 238.1 mmol / hr (10 g / hour).
After the supply of propylene was completed, the temperature was raised to 50 ° C. and maintained for 2 hours, and then the residual gas was purged to recover a prepolymerized catalyst slurry from the autoclave. The recovered preliminary polymerization catalyst slurry was allowed to stand, and the supernatant was extracted. 8.5 mL (6.0 mmol) of a solution of triisobutylaluminum in heptane was added to the remaining solid at room temperature, and the mixture was stirred at room temperature for 10 minutes, and dried under reduced pressure to recover 66.6 g of a solid catalyst.
The prepolymerization magnification (value obtained by dividing the amount of the prepolymerized polymer by the amount of the solid catalyst) was 2.22.

Production of Propylene Homopolymer After sufficiently replacing the inside of a stirred 3.9 L internal volume autoclave with nitrogen, hexane (Wako Pure Chemical Industries, Ltd., a special grade reagent passed through an MS packed column to remove water) was used. 20 ml of diluted triisobutylaluminum (TiBA) was added. Next, 300 ml of hydrogen and then 750 g of liquid propylene were introduced, and the temperature was raised to 70 ° C. and maintained at that temperature. The concentration of hexane-diluted TiBA was 0.1 mmol-Al / ml.
Next, the prepolymerized catalyst obtained above was slurried in hexane (manufactured by Wako Pure Chemical Industries, Ltd., which was prepared by passing a special-grade reagent through an MS-packed column to remove water), and used as a catalyst (excluding the weight of the prepolymerized polymer). ) 40 mg was injected to initiate polymerization. The temperature in the tank was maintained at 70 ° C. One hour later, 5 ml of ethanol was added, the residual gas was purged, and the obtained polymer was dried. As a result, 218 g of a polymer was obtained. The catalyst activity was 5450 g-PP / g-catalyst · h, and the activity for Example 5 was 120%. MFR = 160 (g / 10 minutes).

[Example 5] Production of propylene homopolymer Polymerization was carried out under the same conditions as in Olefin Polymerization Example 3, except that the hexane diluted with TiBA was changed to recovered hexane D. Therefore, the concentration of hexane-diluted TiBA is 0.1 m
mol-Al / ml. Here, the recovered hexane D is a recovered solvent used in a Ziegler-Natta catalyst manufacturing plant, specifically, a solvent used again in the plant via a distillation column and an MS packed column.
As a result, 182 g of a polymer was obtained. The catalyst activity was 4550 g-PP / g-catalyst · h. MFR was 223 (g / 10 minutes). When the halogen content in the recovered hexane D was measured, Cl was 0.70 ppm. When the specific gravity of the TiBA hexane solution is calculated by approximating 0.66, the total number of moles of Cl at the time of polymerization is 0.26 μmol, and the molar ratio of Cl atoms to hafnium atoms of the complex is 0.21 (gram atomic weight). .

[Example 6] Production of propylene homopolymer Polymerization was carried out under the same conditions as in Example 5, except that an additional 20 ml of recovered hexane D was added.
As a result, 150 g of a polymer was obtained. The catalyst activity was 3750 g-PP / g-catalyst · h, and the activity for Example 5 was 82%. MFR was 307 (g / 10 minutes). The total number of moles of Cl at the time of polymerization is 0.52 μmol, and the molar ratio of Cl atoms to hafnium atoms of the complex is 0.42 (gram atomic weight).

[Comparative Example 6] Production of propylene homopolymer Polymerization was carried out under the same conditions as in Olefin Polymerization Example 3, except that 0.0012 mmol of n-butyl chloride was added.
As a result, 76 g of a polymer was obtained. The catalyst activity was 1905 g-PP / g-catalyst-hour, and the activity for Example 5 was 42%. MFR was 803 (g / 10 minutes). The molar ratio of Cl atoms to hafnium atoms in the complex is 0.99 (gram atomic weight).

[Olefin polymerization example 4] Preparation of catalyst and prepolymerization Preparation of catalyst 1130 g of distilled water and 750 g of 96% sulfuric acid were added to a Zeppable flask, the internal temperature was kept at 90 ° C, and granulated monomorillonite having an average particle size of 25 µm was added thereto. 300 g (Benclay SL manufactured by Mizusawa Chemical Co., Ltd.) was added and reacted for 5 hours. The mixture was cooled to room temperature for 1 hour, and washed with distilled water until the pH became 3.69. The washing magnification at this time was 1/10000 or less. The solid at this stage was partially dried, and the elution rate by acid treatment was determined to be 33.5%.
211 g of lithium sulfate monohydrate was dissolved in 521 g of distilled water, and 100 g (dry weight) of the solid obtained by the above acid treatment was added, followed by stirring at room temperature for 120 minutes. This slurry was filtered, and 3000 g of distilled water was added to the obtained solid, followed by stirring at room temperature for 5 minutes. Further, this slurry was filtered, 2500 g of distilled water was added to the obtained solid, and the mixture was stirred for 5 minutes and filtered again. This operation was repeated four more times. The obtained solid was preliminarily dried at 130 ° C. for 2 days under a nitrogen gas stream, coarse particles of 53 μm or more were removed, and further dried at 200 ° C. for 2 hours under reduced pressure to obtain a chemically treated monomorillonite.
The chemically treated monomorillonite was heated at 200 ° C. under reduced pressure for 2 hours. Further, 200 g of the dried montmorillonite obtained above was introduced into a glass reactor having an internal volume of 3 L and equipped with a stirring blade, normal heptane and a heptane solution of triethylaluminum (10 mmol) were added, and the mixture was stirred at room temperature. After 1 hour, the slurry was washed with normal heptane (residual liquid ratio less than 1%) to prepare a slurry of 2000 ml.
Next, a toluene slurry 87 of 3 mmol of (r) -dimethylsilylenebis [2-methyl-4- (4-chlorophenyl) -4H-azulenyl] zirconium dichloride was prepared.
A mixture of 0 ml and 42.6 ml of a heptane solution of triisobutylaluminum (30 mmol) reacted at room temperature for 1 hour was added to the monomorillonite slurry and stirred for 1 hour.

Preliminary Polymerization Subsequently, 2.1 L of normal heptane was introduced into a stirred autoclave having an internal volume of 10 L, which was sufficiently substituted with nitrogen, and kept at 40 ° C. Thereto, the previously prepared monomorillonite / complex slurry was introduced. When the temperature was stabilized at 40 ° C., propylene was supplied at a rate of 100 g / hour, and the temperature was maintained at 40 ° C. After 4 hours, the supply of propylene was stopped and maintained for 2 hours. About 3 L of the supernatant was removed from the recovered preliminary polymerization catalyst slurry, 170 ml of a heptane solution of triisobutylaluminum (30 mmol) was added, and the mixture was stirred for 10 minutes, and then heat-treated at 40 ° C. under reduced pressure. By this operation, a prepolymerized catalyst containing 2.06 g of polypropylene per 1 g of the catalyst was obtained.

Production of Propylene-Ethylene Random Copolymer After sufficiently replacing the inside of a 2.4 L stirred autoclave with nitrogen, water was removed by passing a hexane (special grade reagent manufactured by Wako Pure Chemical Industries, Ltd., through an MS packed column) to remove water. Was diluted with 4 ml of triisobutylaluminum (TiBA). Next, 16 g of ethylene, 30 ml of hydrogen, and 750 g of liquid propylene were introduced, and the temperature was raised to 70 ° C. and maintained at that temperature. The concentration of hexane-diluted TiBA was 0.5 mmol-Al / ml. Next, the prepolymerized catalyst obtained above was slurried in hexane (manufactured by Wako Pure Chemical Industries, Ltd., which was prepared by passing a special-grade reagent through an MS-packed column to remove water), and used as a catalyst (excluding the weight of the prepolymerized polymer). ) 1
5 mg was injected to initiate polymerization. The temperature in the tank was maintained at 70 ° C. One hour later, 5 ml of ethanol was added, the residual gas was purged, and the obtained polymer was dried. As a result, 272 g of a polymer was obtained.
The catalytic activity was 18100 g-PP / g-catalyst.h, and the activity for Example 7 was 11
It was 2%. The MFR was 7.2 (g / 10 minutes), and the ethylene content was 1.9% by weight. When the halogen content in the special grade hexane was measured, it was not detected.

[Example 7]: Production of propylene-ethylene random copolymer Polymerization was carried out under the same conditions as in Olefin polymerization example 4, except that the hexane diluted with TiBA was changed to recovered hexane D. Therefore, the concentration of hexane-diluted TiBA is 0.5 mmol-Al / ml.
As a result, 241 g of a polymer was obtained. The catalyst activity was 16100 g-PP / g-catalyst · h. The MFR was 15 (g / 10 minutes), and the ethylene content was 1.9% by weight.
Here, the Cl content in the recovered hexane D is 0.70 wtppm as described above. According to the description of “1. Preparation of catalyst” in Olefin Polymerization Example 4, the metal content in the catalyst was 200 g of montmorillonite with respect to 3 mmol of the complex, and was 15 μmol / g-montmorillonite, and 15 mg of the complex introduced into the reactor was used. Therefore, it can be calculated as 2.25 × 10 ⁻⁷ (mol). Further, the number of moles of chlorine atoms approximates the specific gravity of the TiBA hexane solution to 0.66,
Chlorine atomic weight (mol) = 4 (ml) x 0.66 (g / ml) x 0.70 (wtppm) /35.5 = 5.21 x ^10-8 (mol)
Can be calculated. Therefore,
It can be calculated that chlorine atom / metal atom (mol / mol) in the reactor = 5.21 × 10 ⁻⁸ /2.25×10 ⁻⁷ = 0.23. Therefore, the molar ratio of Cl atoms to hafnium atoms in the complex is 0.23 (gram atomic weight).

Example 8
Polymerization was carried out under the same conditions as in Example 7, except that the concentration of the recovered hexane D-diluted product of TiBA was 0.25 mmol-Al / ml.
As a result, 219 g of a polymer was obtained. The catalyst activity was 14,600 g-PP / g-catalyst · h, and the activity for Example 7 was 91%. The MFR was 38 (g / 10 minutes), and the ethylene content was 1.9% by weight. The molar ratio of Cl atoms to the complex is 0.46.

[Example 9]
Polymerization was carried out under the same conditions as in Example 7, except that the amount of catalyst added was changed to 10 mg. As a result, 122 g of a polymer was obtained. The catalyst activity was 12200 g-PP / g-catalyst · h, and the activity with respect to Example 7 was 76%. The MFR was 53 (g / 10 minutes), and the ethylene content was 1.9% by weight. The molar ratio of Cl atoms to the complex is 0.69.

[Comparative Example 7]
Polymerization was carried out under the same conditions as in Example 7, except that the concentration of the recovered hexane D-diluted product of TiBA was 0.1 mmol.
As a result, 97 g of a polymer was obtained. The catalyst activity was 6500 g-PP / g-catalyst · h, and the activity for Example 7 was 40%. The MFR was 107 (g / 10 minutes), and the ethylene content was 1.9% by weight. The molar ratio of Cl atoms to the complex is 1.16.

[Comparative Example 8]
Polymerization was carried out under the same conditions as in Olefin Polymerization Example 4, except that 0.5 mg of Chesterton 900 Gold End (manufactured by Chesterton: sealant for flange gasket) was added to the polymerization tank. Chesterton 900 Gold End contains 10 to 15% by weight of polychlorotrifluoroethane.
As a result, 39 g of a polymer was obtained. The catalyst activity was 2600 g-PP / g-catalyst · h, and the activity for Example 7 was 16%. The MFR was 315 (g / 10 minutes), and the ethylene content was 1.9% by weight. The molar ratio of Cl atom to complex is 1.9 to 2.9, and the molar ratio of F atom to complex is 5.7 to 8.7. Note that no other halogen atoms (Br, I) were detected.

[Comparative Example 9]
Polymerization was carried out under the same conditions as in Olefin Polymerization Example 4, except that 0.1 mmol of diethylaluminum chloride was added.
As a result, 22 g of a polymer was obtained. The catalyst activity was 1500 g-PP / g-catalyst · h, and the activity for Example 7 was 9%. MFR was too high to be measured and the ethylene content was 1.9% by weight. The molar ratio of Cl atoms to the complex is 444.

[Olefin polymerization example 5] Catalyst preparation and prepolymerization 500 g of distilled water and 249 g (5.93 mol) of lithium hydroxide monohydrate were charged into a 5 L separable flask equipped with a stirring blade and a reflux device, and a lithium hydroxide aqueous solution was added. Was prepared. Separately, 581 g (5.93 mol) of sulfuric acid was diluted with 500 g of distilled water, and added dropwise to the aqueous lithium hydroxide solution using a dropping funnel. Thereto, 350 g of commercially available granulated montmorillonite (Benclay SL, manufactured by Mizusawa Chemical Co., Ltd., average particle size: 28.0 μm) was further added and stirred. Thereafter, the temperature was raised to 108 ° C. over 30 minutes and maintained for 150 minutes. Furthermore, it cooled to 50 degreeC over 1 hour. The cake was recovered from the slurry by vacuum filtration. 4. Pure water
The slurry was re-slurried by adding 0 L, and the cake was collected by filtration. This operation was repeated four more times.
The recovered cake was dried overnight at 110 ° C. under a nitrogen atmosphere. As a result, 275 g of chemically treated montmorillonite was obtained. The produced chemically treated montmorillonite was dried under reduced pressure at 200 ° C. for 4 hours.
200 g of the chemically treated montmorillonite obtained above was introduced into an autoclave having an inner volume of 10 L, and 1160 ml of heptane and 840 ml (0.5 mol) of a heptane solution of triethylaluminum (0.6 mmol / ml) were added thereto over 30 minutes, and 25 ° C. For 1 hour. Thereafter, the slurry was allowed to settle statically, 1300 ml of the supernatant was extracted, and then washed twice with 2600 ml of heptane, and heptane was added to adjust the total amount of heptane to 1200 ml finally.
Next, 2.97 g (3.9 mmol) of dimethylsilylenebis {2-ethyl-4- (2-fluoro-4-biphenyl) -4H-azulenyl} hafnium dichloride and 516 ml of heptane were charged into a 2 L flask and stirred well. Thereafter, 42 ml (5.9 g) of a heptane solution of triisobutylaluminum (140 mg / ml) was added at room temperature, and the mixture was stirred for 60 minutes. Subsequently, the above solution was introduced into the montmorillonite slurry previously prepared in the autoclave, and stirred for 60 minutes. Heptane was further introduced until the total volume became 5 L, and kept at 30 ° C.
Propylene was introduced therein at a constant rate of 100 g / hr at 40 ° C. for 4 hours, and then maintained at 50 ° C. for 2 hours. The prepolymerized catalyst slurry was recovered by siphon, and after removing the supernatant, the slurry was dried at 40 ° C. under reduced pressure. By this operation, a prepolymerized catalyst containing 2.0 g of polypropylene per 1 g of the catalyst was obtained.

Production of propylene homopolymer
Gas phase copolymerization of propylene was performed using the prepolymerized catalyst obtained above. That is, heptane (special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) is passed through a MS packed column to a continuous gas phase polymerization reactor in which a mixed gas of propylene and hydrogen (hydrogen / propylene = 0.026%) is circulated to remove water. Removed) slurry catalyst and heptane diluted TiBA (concentration 0.01 g / ml) were intermittently fed. The supply amounts were such that the catalyst component (the amount excluding the pre-polymerized polymer) was 75 mg / h and the TiBA was 1 g / h. The conditions for the polymerization reaction were 80 ° C., the partial pressure of propylene was 2.1 MPa, and the average residence time was 6.4 hours.
The average polymerization rate of the produced polypropylene was 240 g / h, the catalytic activity was 3200 g-PP / g-catalyst · h, and the MFR was 59 (g / 10 min). When the halogen content in the special grade heptane was measured, it was not detected.

[Example 10]
Polymerization was carried out under the same conditions as in Olefin Polymerization Example 5, except that recovered heptane C was used as the heptane for diluting TiBA.
The average polymerization rate of the produced polypropylene was 210 g / h, the catalyst activity was 2800 g-PP / g-catalyst · h, and the MFR was 83 (g / 10 min). When the Cl content in the recovered heptane B was measured, it was 0.14 ppm. The molar ratio of Cl atoms to the complex is 0.24.

[Comparative Example 10]
Polymerization was carried out under the same conditions as in Example 10 except that the diluting solvent for TiBA added to the polymerization tank was changed to the recovered hexane D used in Example 7.
The average polymerization rate of the produced polypropylene was 100 g / h, the catalytic activity was 1300 g-PP / g-catalyst · h, and the MFR was 233 (g / 10 min). The molar ratio of Cl atoms to the complex is 1.12.
The data of the results of each of the above polymerization examples, examples and comparative examples are summarized in Tables 1 and 2.

Here, as described above, Examples 1 and 2 and Comparative Examples 1 and 2 are based on Polymerization Example 1 of olefin, and Examples 3 to 4 and Comparative Examples 3 to 5 are Polymerization Example 2 of olefin. It is based on. Examples 5 to 6 and Comparative Example 6 are based on Polymerization Example 3 of olefin. Furthermore, Examples 7 to 9 and Comparative Examples 7 to 9 are based on Polymerization Example 4 of olefins, and Example 10 and Comparative Example 10 are based on Polymerization Example 5 of olefins. Therefore, these should be compared as one block.
Polymerization Examples 1 to 5 are laboratory-level standard polymerizations in which a halogenated polymer is present below the detection limit (particularly, as a solvent, a special grade reagent manufactured by Wako Pure Chemical Industries, Ltd. is used in an MS-packed column). As described above, the raw material gas used herein is a halogen-containing compound having a detection level below the detection limit, and the polymerization apparatus is of a laboratory-level clean type.) This is a polymerization in which the recovered solvent is reused in the plant, and a halogen compound derived from the solvent, the raw material monomer and the polymerization apparatus is present, and is a main constituent requirement of the present invention from the experimental data of the molar ratio of the halogen. A value of 0.8 of the halogen molar ratio is specified. In each comparative example, the molar ratio of halogen exceeds 0.8 as specified in the present invention, and is compared with each example. As described above, in each of Examples and Comparative Examples, F, Br, and I among the halogens were all below the detection limit.
The molar ratio of the halogen represents the ratio of the gram atomic weight of the impurity halogen to the transition metal of the metallocene catalyst, which is the basic constitution of the present invention. The activity (%) in each table represents the ratio (%) of each example described in Tables 1 and 2 to the reference example (base example), for example, the catalytic activity of Example 1. . MFR is a physical property index widely used in polyolefins, and is a measure of molecular weight and moldability. The lower the numerical value, the higher the molecular weight and the lower the melt fluidity during molding.

[Consideration of results of Examples and Comparative Examples]
By contrasting each of the above Examples and Comparative Examples, in the present invention, it is possible to realize polymerization having excellent catalytic activity and high polymerization efficiency, and it is possible to produce a polymer having a high molecular weight from the MFR value and suitable for moldability. it is obvious.
Further, it is rationally proved from each data that the ratio of the gram atomic weight of the impurity halogen to the transition metal of the metallocene catalyst, which is the basic constitution of the present invention, is 0.8 or less.
Specifically, in the polymerization of propylene, Example 1 sets the molar ratio of halogen to be much lower than the specified value of 0.8 according to the present invention, thereby achieving a polymerization level close to that of Polymerization Example 1 of a laboratory-level clean polymerization example. The reaction was carried out, and the result was not inferior to Polymerization Example 1 in catalytic activity. In Example 2, the molar ratio of halogen is higher than that of Example 1, but the molar ratio of 0.1 according to the present invention is not limited.
Since it is 8 or less, a value close to that of Example 1 is obtained in the catalytic activity. Examples 1 and 2 also show that the molar ratio of halogen is more preferably 0.6 or less. This tendency is the same in the polymerization of ethylene, and is evident by comparing Examples 3 to 4 with Comparative Examples 3 to 5 based on Polymerization Example 2. Furthermore, the molecular weight of the polymer was more excellent in the examples. Regarding the superiority of the molecular weight, the same effect was also confirmed for the polymerization results of propylene, and it was confirmed that Examples 5 to 6 and Comparative Examples 6 and Examples 7 to 9 and Comparative Examples 7 to 9 and Examples This is apparent from the comparison between Comparative Example 10 and Comparative Example 10. In Comparative Example 9, since the halogen molar ratio was very high, the catalytic activity was very poor as compared with each Example, and the MFR value was not measurable and a practical polymer was not formed. ing.
Further, it has been confirmed from the results of polymerization using different catalyst systems through Examples and Comparative Examples that the present invention can be applied to metallocene catalyst systems with versatility.

Claims (10)

In producing a polyolefin by polymerizing an olefin using a single-site catalyst, the gram atomic weight of a halogen atom derived from a halogen-containing compound mixed into the polymerization reaction other than a halogen atom derived from a catalyst component is introduced. An improved method for producing a polyolefin, comprising controlling the amount of a halogen-containing compound to be 0.8 or less based on the gram atomic weight of a transition metal of a site catalyst. The method for improving polyolefin production according to claim 1, wherein the single-site catalyst is a metallocene catalyst comprising the following components (A) and (B) and, if necessary, (C).
Component (A): Metallocene complex Component (B): Promoter Component (C): Organoaluminum compound (excluding organoaluminum halide compound) The method for improving polyolefin production according to claim 1 or 2, wherein the olefin is obtained by polymerizing or copolymerizing an α-olefin having 3 or more carbon atoms. The transition metal complex component of the metallocene complex in the metallocene catalyst is a transition metal compound belonging to Groups 4 to 6 of the periodic table having a conjugated five-membered ring ligand, The method according to claim 2 or 3, wherein An improved method for the production of polyolefins. The co-catalyst for activating the metallocene complex in the metallocene catalyst is an aluminum oxy compound, an ionic compound or a Lewis acid, a solid acid, or an ion-exchangeable layered silicate, wherein: Item 5. An improved method for producing a polyolefin according to any one of Items 4. The co-catalyst for activating the metallocene complex is an organoboron compound, and the polyolefin to be produced is one that polymerizes ethylene or propylene, one that copolymerizes ethylene with an α-olefin having 3 or more carbon atoms, or propylene and another carbon number. The method for improving polyolefin production according to any one of claims 2 to 5, wherein two or more α-olefins are copolymerized. In the polymer material, the amount of the organic compound to which the halogen atom is bonded, the amount of the silicon atom-containing compound to which the halogen atom is bonded, the amount of the aluminum atom-containing compound to which the halogen atom is bonded, and the amount of the halogen atom in the organic solvent which is bonded. The polyolefin according to any one of claims 1 to 6, characterized in that it controls any or all of the mixed amount of the compound thus obtained and the mixed amount of the halogen-containing compound which is an impurity from the polymerization apparatus. How to improve manufacturing. The method for improving polyolefin production according to claim 7, wherein the halogen-containing compound as an impurity from the polymerization apparatus is derived from a gasket sealant for the flange. The method for improving polyolefin production according to any one of claims 1 to 8, wherein the halogen is chlorine. When the gram atomic weight of the halogen atom derived from the halogen-containing compound mixed into the polymerization reaction other than the halogen atom derived from the catalyst component exceeds 0.8 with respect to the gram atomic weight of the transition metal, 0.8 or less. The method for improving the production of a polyolefin according to any one of claims 1 to 9, wherein the amount of the halogen-containing compound present in the polymerization reaction is reduced so as to maintain the value.