JP2016089107A - METHOD FOR POLYMERIZING α-OLEFINS - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing polymers of α-olefins with a high catalytic activity.SOLUTION: The method for producing polymers of α-olefins by using a catalyst including (A) a solid catalyst including magnesium, titanium, halogen and a succinate compound as an inner electron donor compound and (B) an organoaluminum compound and including no external electron donor compound comprises a step of bringing the component (A) into contact with the component (B) to prepare the catalyst and a step of bringing the catalyst into contact with α-olefins in which when the time until the catalyst is brought into contact with α-olefins after preparing the catalyst by bringing the component (A) into contact with the component (B)is represented as τ, the τ is 180 seconds or less.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for polymerizing α-olefins.

  A number of prior arts disclose methods for producing a crystalline polyolefin by polymerizing an α-olefin such as propylene and 1-butene in the presence of a stereoregular catalyst. Among these methods, (a) a solid catalyst containing magnesium, titanium, halogen and an electron donor compound as essential components, (b) an organoaluminum compound and (c) a catalyst formed from an electron donor compound. Methods for obtaining highly stereoregular polymers with high catalytic activity by polymerizing α-olefins are disclosed in prior art documents (for example, Patent Documents 1 to 4) and adopted on an industrial scale. However, there is a need in the art for further high catalytic activity polymerization techniques.

  Patent Document 5 (Japanese Patent Laid-Open No. 2013-14725) describes (a) a solid catalyst component, (b) an organoaluminum compound, and (c) an electron donor compound in a specific order for the purpose of achieving high catalytic activity. A polymerization process in which the catalyst is contacted is disclosed. Specifically, Patent Document 5 discloses that a prepolymerized catalyst is obtained by prepolymerizing an α-olefin using (a) a solid catalyst component in the presence of a small amount of (b) an organoaluminum compound, Disclosed is a method in which an α-olefin is polymerized after contacting a contact product obtained by previously contacting an organoaluminum compound and (c) an electron donor compound before polymerizing the α-olefin. To do.

Japanese Patent No. 2637076 Patent No. 2740503 Patent No. 3984304 No. 6-23406 JP 2013-14725 International Publication No. 2009/069483 International Publication No. 2009/057747 JP-A-2005-306910 JP 2004-131537 A Special table 2002-542347

  In this field, a method for producing an α-olefin polymer with higher catalytic activity is desired. Therefore, an object of the present invention is to provide a method for producing a polymer of α-olefins with high catalytic activity.

From the point of time when the catalyst was prepared by bringing (A) magnesium, titanium, halogen, and a solid catalyst containing a succinate compound as an internal electron donor compound into contact with (B) an organoaluminum compound. Focusing on the time τ until it is brought into contact with α-olefins, it has been found that the above problem can be solved when the τ is equal to or less than a specific time.
That is, the said subject is solved by the following this invention.
[1] (A) A solid catalyst containing magnesium, titanium, halogen, and a succinate compound as an internal electron donor compound, and (B) a catalyst containing an organoaluminum compound and no external electron donor compound. A process for producing a polymer of α-olefins, comprising:
Contacting the components (A) and (B) to prepare the catalyst, and contacting the catalyst with α-olefins,
When τ is the time from when the components (A) and (B) are contacted to prepare the catalyst until the catalyst is contacted with the α-olefins, the τ is 180 seconds or less.
The manufacturing method.
[2] The production method according to [1], wherein τ is 3 to 180 seconds.
[3] The production method according to [1] or [2], wherein the temperature at which each component in the catalyst preparation step is brought into contact is 3 to 30 ° C.
[4] The production method according to [1] or [2], wherein the temperature at which the components in the catalyst preparation step are brought into contact with each other is 3 to 20 ° C.
[5] A reactor for the production method according to [1] above,
A polymerization reactor, and an introduction device for introducing the catalyst into the reactor,
A reaction apparatus comprising a contact portion for preparing the catalyst by bringing the introduction device into contact with components (A) and (B).

  According to the present invention, a polymer of α-olefins can be produced with high catalytic activity.

Schematic diagram showing the production method of the present invention The figure which shows the result of an example and a reference example

  Hereinafter, the present invention will be described in detail. In the present invention, “X to Y” includes X and Y, that is, values at both ends. In the present invention, “X or Y” means either X or Y, or both X and Y.

1. Manufacturing method (1) τ
In the production method of the present invention, the catalyst is prepared by contacting (A) a solid catalyst containing magnesium, titanium, halogen, and a succinate compound as an internal electron donor compound, and (B) an organoaluminum compound. Τ is 180 seconds or less, where τ is the time from contact to α-olefins. An outline of the production method of the present invention is shown in FIG.

  The step of bringing components (A) and (B) into contact can be carried out as known. For example, both can be brought into contact using a pipe, a metal container, a metal container with a stirrer, and the like. The compounding ratio of the component (A) and the component (B) is preferably 30 to 3000 mol of the component (B) with respect to 1 mol of Ti atoms contained in the component (A). It can also change depending on. Usually, the upper limit of the temperature for contacting both is preferably 50 ° C. or less, more preferably 40 ° C. or less, further preferably 30 ° C. or less, and further preferably 28 ° C. or less. The lower limit is preferably 3 ° C or higher, more preferably 10 ° C or higher, and further preferably 13 ° C or higher. If the temperature is too high, the catalyst tends to deteriorate, and if the temperature is too low, the cost for cooling increases. Contacting can also be carried out in an inert solvent. Examples of the inert solvent include hydrocarbon compounds such as butane, pentane, hexane, heptane, octane, benzene, toluene, and xylene ethylbenzene.

  By this contact, the catalyst used in the present invention can be quickly prepared. When the scale is large, all the raw materials may not be converted to the catalyst, but the time at which a part of the catalyst is generated is referred to as the time when the catalyst is prepared. Therefore, the time when the catalyst is prepared is also the time when the components (A) and (B) start to contact. This time is referred to as τ0 for convenience.

  The catalyst is then contacted with α-olefins. The process of making it contact can be implemented as well-known. For example, both can be contacted by dropping the catalyst into α-olefins charged in the reactor. For convenience, the contact start time with the α-olefins is denoted by τ1. From this point of time, the α-olefins can be polymerized.

  The τ is the time from when the catalyst is prepared until it is used, and is defined as τ1-τ0. That is, τ is “a catalyst unused time”. When preparing a catalyst in a container, (tau) can be adjusted with the residence time. When adjusting the catalyst in the pipe, τ can be adjusted by changing the length and thickness of the pipe.

  In the present invention, the τ is set to 180 seconds or less. Thus, by shortening τ, the activity of the catalyst can be kept high. In this respect, the upper limit of τ is preferably 100 seconds or less, and more preferably 50 seconds or less. The lower limit of τ may be 0 seconds or more. That τ is 0 seconds means that catalyst preparation and contact between the catalyst and α-olefins occur simultaneously. For example, τ = 0 seconds can be achieved by charging α-olefins and the component (B) in the reactor and dropping the component (A) into the reactor. However, the lower limit of τ is preferably 3 seconds or more, and more preferably 5 seconds or more.

  In the prior art, the concept of τ itself did not exist. Furthermore, conventionally, when a succinate compound is used as the internal electron donor compound, it is common to use an external electron donor compound together. In the present invention, the concept of τ was found in a catalyst system that does not use an external electron donor compound, and high activity was successfully achieved by making τ within a specific time. This mechanism is not clear and is not limited, but it is presumed that when τ is long, titanium in component (A) is easily overreduced by component (B) organoaluminum compound and the like, and the activity decreases. Further, in the present invention, since an external electron donor compound is not used, it can be produced at a low cost, and the activity is increased as compared with the case of using an external electron donor. Furthermore, although the stereoregularity is lower than when an external electron donor compound is used, in the field of films and sheets, the low stereoregularity is important in order to improve transparency, molding processability, impact resistance, etc. Since coalescence may be preferred, the present invention is effectively used in the art.

(2) Each component 1) Component (A)
The solid catalyst component contains magnesium, titanium, halogen and an electron donor compound as essential components. Regarding this solid catalyst component, many prior art documents have proposed the manufacturing method. Specifically, this solid catalyst component can be obtained by bringing a magnesium compound, a titanium compound and an electron donor compound into contact with each other. For example, the following method is known.
(1) A magnesium compound or a complex compound of a magnesium compound and an electron donor compound was pretreated with or without a pretreatment with a reaction aid such as an electron donor compound, an organoaluminum compound or a halogen-containing silicon compound. A method of reacting a solid with a titanium compound that forms a liquid phase under reaction conditions (the complex compound may be used after being pulverized in the presence or absence of an electron donor compound, a pulverization aid, etc. May be used without crushing),
(2) A method of depositing a solid titanium composite by reacting a liquid magnesium compound with a liquid titanium compound in the presence or absence of an electron donor compound,
(3) A method of reacting a solid magnesium compound with a liquid titanium compound and an electron donor compound,
(4) A method of further reacting a titanium compound with the one obtained in (2) or (3) above,
(5) A method of further reacting an electron donor compound and a titanium compound with those obtained in (1), (2) and (3) above,
(6) A magnesium compound or a complex compound of a magnesium compound and an electron donor compound is pulverized in the presence of an electron donor compound and a titanium compound, such as an electron donor compound, an organoaluminum compound, or a halogen-containing silicon compound. A method of treating a solid obtained with or without pretreatment with a reaction aid with a halogen, a halogen compound or an aromatic hydrocarbon (the grinding may be carried out in the presence of a grinding aid or the like) ,
(7) A method of treating the compound obtained in the above (1) to (5) with a halogen, a halogen compound, or an aromatic hydrocarbon.

As a titanium compound used for preparation of a component (A), the tetravalent titanium compound represented by general formula: Ti (OR) _{gX4 -g} is suitable. In the formula, R is a hydrocarbon group, X is a halogen, and 0 ≦ g ≦ 4. As titanium compounds, TiCl ₄ and more specifically, TiBr _4, titanium tetrahalides such as _{TiI 4; Ti (OCH 3)} Cl 3, Ti (OC 2 H 5) Cl 3, Ti (O n -C 4 H _{9) Cl 3, Ti (OC} 2 H 5) Br 3, Ti (OisoC 4 H 9) trihalide, alkoxy titanium such as _{Br 3; Ti (OCH 3)} 2 Cl 2, Ti (OC 2 H 5) 2 Cl ₂ , Di (halogenated alkoxytitanium) such as Ti (O _n —C ₄ H ₉ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Br ₂ ; Ti (OCH ₃ ) ₃ Cl, Ti (OC ₂ H ₅ ) ₃ Cl _{, Ti (O n -C 4 H} 9) 3 Cl, Ti (OC 2 H 5) 3 monohalogenated trialkoxy titanium such as _{Br; Ti (OCH 3) 4} , Ti (OC 2 H 5) _{4, Ti (O n -C 4} H 9) 4 and the like tetraalkoxytitanium such. Among these, preferred are halogen-containing titanium compounds, particularly titanium tetrahalides, and more particularly preferred is titanium tetrachloride.

  Magnesium compounds used for the preparation of component (A) include magnesium compounds having a magnesium-carbon bond or magnesium-hydrogen bond, such as dimethylmagnesium, diethylmagnesium, dipropylmagnesium, dibutylmagnesium, diamylmagnesium, dihexylmagnesium, Examples include decylmagnesium, ethylmagnesium chloride, propylmagnesium chloride, butylmagnesium chloride, hexylmagnesium chloride, amylmagnesium chloride, butylethoxymagnesium, ethylbutylmagnesium, butylmagnesium hydride and the like. These magnesium compounds can also be used, for example, in the form of a complex compound with organic aluminum or the like, and may be liquid or solid. Further preferred magnesium compounds include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, magnesium fluoride; methoxy magnesium chloride, ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy magnesium chloride, octoxy magnesium chloride, and the like. Alkoxymagnesium halides; aryloxymagnesium halides such as phenoxymagnesium chloride and methylphenoxymagnesium chloride; alkoxymagnesiums such as ethoxymagnesium, isopropoxymagnesium, butoxymagnesium, n-octoxymagnesium and 2-ethylhexoxymagnesium; phenoxy Allyloxy Magnesium like Magnesium, Dimethylphenoxy Magnesium ; Magnesium laurate, such as carboxylic acid salts of magnesium such as magnesium stearate and the like.

  The electron donor compound used for the preparation of component (A) is generally referred to as “internal electron donor”. In the present invention, a succinate compound is used as the internal electron donor. The succinate compound is a diester of succinic acid or a succinic acid derivative. Hereinafter, the succinate compound will be described in detail. The succinate compound preferably used in the present invention is represented by the following formula (I).

In which the radicals R ₁ and R ₂ are identical or different from one another and optionally contain heteroatoms, a C1-C20 linear or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl or alkylaryl group. The groups R _{3 to} R ₆ are the same or different from each other and are C ₁ -C 20 linear or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl, or hydrogen, or optionally containing a heteroatom, or The groups R _{3 to} R ₆ which are alkylaryl groups and are bonded to the same carbon atom or different carbon atoms may be bonded together to form a ring.
R ₁ and R ₂ are preferably C1-C8 alkyl, cycloalkyl, aryl, arylalkyl, and alkylaryl groups. Particularly preferred are compounds wherein R ₁ and R ₂ are selected from primary alkyls, especially branched primary alkyls. Examples of suitable R ₁ and R ₂ groups are C2 to C8 alkyl groups such as methyl, ethyl, n-propyl, n-butyl, isobutyl, neopentyl, 2-ethylhexyl. Ethyl, isobutyl, and neopentyl are particularly preferred.

One preferred group of compounds represented by formula (I) are branched alkyl, cycloalkyl, aryl, arylalkyl, wherein R _{3 to} R ₅ are hydrogen and R ₆ has 3 to 10 carbon atoms. And an alkylaryl group. Preferred specific examples of such mono-substituted succinate compounds include diethyl-sec-butyl succinate, diethyl hexyl succinate, diethyl cyclopropyl succinate, diethyl norbornyl succinate, diethyl perihydrosuccinate, diethyl Trimethylsilyl succinate, diethyl methoxy succinate, diethyl-p-methoxyphenyl succinate, diethyl-p-chlorophenyl succinate, diethyl phenyl succinate, diethyl cyclohexyl succinate, diethyl benzyl succinate, diethyl cyclohexyl Methyl succinate, diethyl-t-butyl succinate, diethyl isobutyl succinate, diethyl isopropyl succinate, diethyl neopentyl succinate, diethyl isopenty Succinate, diethyl (1-trifluoromethylethyl) succinate, diethyl fluorenyl succinate, 1- (ethoxycarbodiisobutylphenyl succinate, diisobutyl-sec-butyl succinate, diisobutyl texyl succinate, diisobutyl cyclopropyls Succinate, diisobutyl norbornyl succinate, diisobutyl perhydrosuccinate, diisobutyltrimethylsilyl succinate, diisobutyl methoxy succinate, diisobutyl-p-methoxyphenyl succinate, diisobutyl-p-chlorophenyl succinate, diisobutyl cyclohexyl Succinate, diisobutylbenzyl succinate, diisobutylcyclohexylmethyl succinate, diisobutyl-t-butyl succinate Diisobutyl isobutyl succinate, diisobutyl isopropyl succinate, diisobutyl neopentyl succinate, diisobutyl isopentyl succinate, diisobutyl (1-trifluoromethylethyl) succinate, diisobutyl fluorenyl succinate, dineopentyl-sec -Butyl succinate, dineopentyl texyl succinate, dineopentyl cyclopropyl succinate, dineopentyl norbornyl succinate, dineopentyl perhydrosuccinate, dineopentyl trimethylsilyl succinate, Neopentyl methoxysuccinate, dineopentyl-p-methoxyphenyl succinate, dineopentyl-p-chlorophenyl succinate, dineopentyl phenyl succinate, di Neopentyl cyclohexyl succinate, dineopentyl benzyl succinate, dineopentyl cyclohexyl methyl succinate, dineopentyl-t-butyl succinate, dineopentyl isobutyl succinate, dineopentyl isopropyl succinate, di Neopentyl neopentyl succinate, dineopentyl isopentyl succinate, dineopentyl (1-trifluoromethylethyl) succinate, dineopentyl fluorenyl succinate.

Another preferred group of compounds within the scope of formula (I) are C ₁ -C 20 linear or branched, wherein at least two groups from R _{3 to} R ₆ are different from hydrogen and optionally contain heteroatoms Selected from alkyl, alkenyl, cycloalkyl, aryl, arylalkyl, or alkylaryl groups. Particularly preferred are compounds in which two groups different from hydrogen are bonded to the same carbon atom. Specifically, R ₃ and R ₄ are different from hydrogen, and R ₅ and R ₆ are hydrogen atoms. Preferred specific examples of such disubstituted succinates are diethyl-2,2-dimethylsuccinate, diethyl-2-ethyl-2-methylsuccinate, diethyl-2-benzyl-2-isopropylsuccinate, diethyl 2-cyclohexylmethyl-2-isobutyl succinate, diethyl-2-cyclopentyl-2-n-butyl succinate, diethyl-2, 2-diisobutyl succinate, diethyl-2-cyclohexyl-2-ethyl succinate , Diethyl-2-isopropyl-2-methylsuccinate, diethyl-2-tetradecyl-2-ethylsuccinate, diethyl-2-isobutyl-2-ethylsuccinate, diethyl-2- (1-trifluoro Methylethyl) -2-methylsuccinate, diethyl-2-isopentyl-2- Sobutyl succinate, diethyl-2-phenyl-2-n-butyl succinate, diisobutyl-2,2-dimethyl succinate, diisobutyl-2-ethyl-2-methyl succinate, diisobutyl-2-benzyl- 2-isopropyl succinate, diisobutyl-2-cyclohexylmethyl-2-isobutyl succinate, diisobutyl-2-cyclopentyl-2-n-butyl succinate, diisobutyl-2,2-diisobutyl succinate, diisobutyl-2 -Cyclohexyl-2-ethyl succinate, diisobutyl-2-isopropyl-2-methyl succinate, diisobutyl-2-tetradecyl-2-ethyl succinate, diisobutyl-2-isobutyl-2-ethyl succinate, diisobutyl -2- (1-trifluoro Tilethyl) -2-methylsuccinate, diisobutyl-2-isopentyl-2-isobutylsuccinate, diisobutyl-2-phenyl-2-n-butylsuccinate, dineopentyl-2,2-dimethylsuccinate, dineopentyl 2-ethyl-2-methyl succinate, dineopentyl-2-benzyl-2-isopropyl succinate, dineopentyl-2-cyclohexylmethyl-2-isobutyl succinate, dineopentyl-2-cyclopentyl-2-n-butyl Succinate, dineopentyl-2,2-diisobutyl succinate, dineopentyl-2-cyclohexyl-2-ethyl succinate, dineopentyl-2-isopropyl-2-methyl succinate, dineopentyl-2-tetradecyl-2-ethyl succinate , Dineopentyl-2-isobutyl-2-ethyl succinate, dineopentyl-2- (1-trifluoromethylethyl) -2-methyl succinate, dineopentyl-2-isopentyl-2-isobutyl succinate, dineopentyl 2-Phenyl-2-n-butyl succinate.

Furthermore, compounds in which at least two groups different from hydrogen are bonded to different carbon atoms are particularly preferred. Specifically, it is a compound in which R ₃ and R ₅ are groups different from hydrogen. In this case, R ₄ and R ₆ may be a hydrogen atom or a group different from hydrogen, but preferably one of them is a hydrogen atom (trisubstituted succinate). Preferred examples of such compounds are diethyl-2,3-bis (trimethylsilyl) succinate, diethyl-2,2-sec-butyl-3-methylsuccinate, diethyl-2- (3,3,3- Trifluoropropyl) -3-methylsuccinate, diethyl-2,3-bis (2-ethylbutyl) succinate, diethyl-2,3-diethyl-2-isopropylsuccinate, diethyl-2,3-diisopropyl-2 -Methyl succinate, diethyl-2,3-dicyclohexyl-2-methyldiethyl-2,3-dibenzyl succinate, diethyl-2,3-diisopropyl succinate, diethyl-2,3-bis (cyclohexylmethyl) ) Succinate, diethyl-2,3-di-t-butylsuccinate, diethyl-2,3-diisobuty Succinate, diethyl-2,3-dineopentyl succinate, diethyl-2,3-diisopentyl succinate, diethyl-2,3- (1-trifluoromethylethyl) succinate, diethyl-2,3- Tetradecyl succinate, diethyl-2,3-fluorenyl succinate, diethyl-2-isopropyl-3-isobutyl succinate, diethyl-2-tert-butyl-3-isopropyl succinate, diethyl-2- Isopropyl-3-cyclohexyl succinate, diethyl-2-isopentyl-3-cyclohexyl succinate, diethyl-2-tetradecyl-3-cyclohexylmethyl succinate, diethyl-2-cyclohexyl-3-cyclopentyl succinate, diisobutyl -2,3-diethyl-2-iso Lopyl succinate, diisobutyl-2,3-diisopropyl-2-methyl succinate, diisobutyl-2,3-dicyclohexyl-2-methyl succinate, diisobutyl-2,3-dibenzyl succinate, diisobutyl-2 , 3-diisopropyl succinate, diisobutyl-2,3-bis (cyclohexylmethyl) succinate, diisobutyl-2,3-di-t-butyl succinate, diisobutyl-2,3-diisobutyl succinate, diisobutyl-2 , 3-Dineopentyl succinate, diisobutyl-2,3-diisopentyl succinate, diisobutyl-2,3- (1-trifluoromethylethyl) succinate, diisobutyl-2,3-tetradecyl succinate Diisobutyl-2,3-fluorenylsuccinate Diisobutyl-2-isopropyl-3-isobutyl succinate, diisobutyl-2-tert-butyl-3-isopropyl succinate, diisobutyl-2-isopropyl-3-cyclohexyl succinate, diisobutyl-2-isopentyl-3- Cyclohexyl succinate, diisobutyl-2-tetradecyl-3-cyclohexylmethyl succinate, diisobutyl-2-cyclohexyl-3-cyclopentyl succinate, dineopentyl-2,3-bis (trimethylsilyl) succinate, dineopentyl-2,2- sec-butyl-3-methyl succinate, dineopentyl-2- (3,3,3-trifluoropropyl) -3-methyl succinate, dineopentyl-2,3-bis (2-ethylbutyl) succinate, cine Pentyl-2,3-diethyl-2-isopropyl succinate, dineopentyl-2,3-diisopropyl-2-methyl succinate, dineopentyl-2,3-dicyclohexyl-2-methyl succinate, dineopentyl-2,3 -Dibenzyl succinate, dineopentyl-2,3-diisopropyl succinate, dineopentyl-2,3-bis (cyclohexylmethyl) succinate, dineopentyl-2,3-di-t-butyl succinate, dineopentyl-2, 3-diisobutyl succinate, dineopentyl-2,3-dineopentyl succinate, dineopentyl-2,3-diisopentyl succinate, dineopentyl-2,3- (1-trifluoromethylethyl) succinate, dineopentyl -2,3-tetradeci Succinate, dineopentyl-2,3-fluorenyl succinate, dineopentyl-2-isopropyl-3-isobutyl succinate, dineopentyl-2-tert-butyl-3-isopropyl succinate, dineopentyl-2-isopropyl-3- They are cyclohexyl succinate, dineopentyl-2-isopentyl-3-cyclohexyl succinate, dineopentyl-2-tetradecyl-3-cyclohexylmethyl succinate, and dineopentyl-2-cyclohexyl-3-cyclopentyl succinate.

Among the compounds of the formula (I), compounds in which some of the groups R _{3 to} R ₆ are bonded together to form a ring can also be preferably used. As such compounds, compounds listed in Patent Document 10, for example, 1- (ethoxycarbonyl) -1- (ethoxyacetyl) -2,6-dimethylcyclohexane, 1- (ethoxycarbonyl) -1- (ethoxyacetyl) ) -2,5-dimethylcyclopentane, 1- (ethoxycarbonyl) -1- (ethoxyacetylmethyl) -2 monomethylcyclohexane, 1- (ethoxycarbonyl) -1- (ethoxy (cyclohexyl) acetyl) cyclohexane. be able to. In addition, for example, a cyclic succinate compound as disclosed in Patent Document 6 can also be suitably used. As an example of another cyclic succinate compound, a compound disclosed in Patent Document 7 is also preferable.

Of the compounds of formula (I), when the groups R _{3 to} R ₆ contain heteroatoms, the heteroatoms may be group 15 atoms including nitrogen and phosphorus atoms or group 16 atoms including oxygen and sulfur atoms. preferable. Examples of the compound in which the groups R _{3 to} R ₆ include a Group 15 atom include compounds disclosed in Patent Document 8. On the other hand, examples of the compound in which the groups R _{3 to} R ₆ include a Group 16 atom include a compound disclosed in Patent Document 9.

  Examples of the halogen atom constituting the solid catalyst component include fluorine, chlorine, bromine, iodine or a mixture thereof, and chlorine is particularly preferable.

2) Component (B)
The following are mentioned as an organoaluminum compound of a component (B).
Trialkylaluminum such as triethylaluminum, tributylaluminum;
Trialkenyl aluminum such as triisoprenyl aluminum:
Dialkylaluminum alkoxides such as diethylaluminum ethoxide and dibutylaluminum butoxide;
Alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide;

Partially alkoxylated alkylaluminum having an average composition such as R _12.5 Al (OR ₂ ) _0.5 ;
Dialkylaluminum halides such as diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide;
Alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide;

Partially halogenated alkylaluminums such as alkylaluminum dihalogenides such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide and the like;
Dialkylaluminum hydrides such as diethylaluminum hydride, dibutylaluminum hydride;
Partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as ethylaluminum dihydride, propylaluminum dihydride;
Partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxychloride, butylaluminum butoxychloride, ethylaluminum ethoxybromide.

3) α-olefins α-olefins refer to α-olefins or derivatives thereof. Examples of the α-olefins include propylene, ethylene, 1-butene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, and 4,4-dimethyl-1. -Α-olefins such as pentene, vinylcyclopentane and vinylcyclohexane; styrene derivatives such as styrene and α-methylstyrene; dienes such as butadiene and 1,9-decadiene; and allyltrialkylsilanes. These may be used in combination. In particular, the present invention exhibits a significant effect in propylene polymerization.

4) Polymerization Polymerization is carried out by bringing the α-olefins into contact with the catalyst prepared as described above. At this time, it is preferable to first perform prepolymerization using the catalyst. Preliminary polymerization is a step of forming a chain of α-olefins, which become a foothold for the subsequent main polymerization of α-olefins, in a solid catalyst component. The prepolymerization can be performed by a known method such as a batch method or a continuous method. In the prepolymerization, the above α-olefins are used as monomers. These monomers can be used not only in one type but also in two or more types in stages or in a mixture. Hydrogen can also be used as a molecular weight modifier during prepolymerization. The prepolymerization can be performed in an inert hydrocarbon solvent, but can also be performed in a liquid monomer or a gas phase monomer.
The prepolymerization is usually performed at 40 ° C or lower, preferably 30 ° C or lower, more preferably 20 ° C or lower. The amount of α-olefin to be prepolymerized is preferably 0.5 to 800 g, more preferably 5 to 500 g, and still more preferably 10 to 400 g with respect to 1 g of the solid catalyst.

  Next, the prepolymerized catalyst is added to a polymerization reaction system charged with α-olefins, and main polymerization of α-olefins is performed. The main polymerization can be carried out by a slurry polymerization method, a gas phase polymerization method, a bulk polymerization method, or a known polymerization method combining these. The polymerization may be batch-wise, semi-continuous, or continuous, but is preferably continuous for industrial use. The polymerization temperature is preferably from room temperature to 150 ° C, more preferably from 40 ° C to 100 ° C. The pressure is generally normal pressure to 10 MPa, and preferably 0.5 to 6 MPa. The polymerization time is usually 10 hours or less, preferably 10 minutes to 5 hours. In the main polymerization, hydrogen can be used as a molecular weight regulator.

(4) Catalytic activity According to the production method of the present invention, a polymer of α-olefins can be obtained with high catalytic activity. Specifically, assuming that the catalyst activity when τ is as long as 1200 to seconds is 1, the present invention can achieve about twice as much catalyst activity. The stereoregularity of the polymer of α-olefins obtained at this time is 93% by weight or more in terms of xylene-insoluble component (XI) when polypropylene is taken as an example.

2. Manufacturing apparatus The manufacturing method of this invention can be implemented using arbitrary apparatuses, unless the effect of invention is impaired. However, it comprises a polymerization reactor and an introduction device for introducing the catalyst into the reactor, and the introduction device comprises a contact portion for preparing the catalyst by bringing the components (A) and (B) into contact with each other. It is preferable to use an apparatus.

  A well-known thing can be used as a polymerization reactor. The contact portion may be a pipe, a metal container, a metal container with a stirrer, or the like. In particular, when the components are made to flow continuously through the pipe and the components are brought into contact with each other in the pipe, the contact time can be adjusted by adjusting the thickness and length of the pipe.

The present invention will be further described below with reference to examples. Each analysis was performed by the following method.
[MFR (melt flow rate)]
According to JIS K 7210, the measurement was performed under conditions of a temperature of 230 ° C. and a load of 21.18 N.

[XI (xylene insoluble component amount)]
A 300 mL flask was charged with 2.5 g of a polymer sample and 250 mL of orthoxylene, and dissolved at the boiling temperature for 30 minutes with stirring. Subsequently, after the solution was allowed to cool to 100 ° C., the flask was placed in a constant temperature water bath at 25 ° C., and filtration was performed after 1 hour had passed since the temperature reached 25 ° C. Orthoxylene in the collected filtrate was evaporated, and the value obtained by dividing the weight of the remaining residue by the weight of the charged polymer sample was multiplied by 100, and the weight% of the polymer soluble in xylene at 25 ° C. was calculated. XI, that is, the amount of xylene-insoluble component (% by weight of the polymer insoluble in xylene at 25 ° C.) is obtained by (100−% by weight of the soluble polymer) and is used as an index of the stereoregularity of the polymer.

[Polymerization activity]
Using 240AA manufactured by Agilent Technologies, the magnesium content in the produced polymer sample was measured by atomic absorption, and the polymerization activity was determined as the polymer polymerization amount per gram of catalyst from the magnesium content contained in the original catalyst. Asked.

[Example 1-1]
(1) Preparation of solid catalyst component A solid catalyst component of component (A) was prepared according to the description in Examples of JP2011-500907A. Specifically, it was prepared as follows.
A 500 mL four-necked round bottom flask purged with nitrogen was charged with 250 mL of TiCl ₄ at 0 ° C. While stirring, 10.0 g of fine spherical MgCl ₂ .2.8C ₂ H ₅ OH and 9.1 mmol of diethyl-2,3- (diisopropyl) succinate were added. MgCl ₂ 2.8C ₂ H ₅ OH was prepared according to the method described in Example 2 of US Pat. No. 4,399,054 operating at 3000 rpm instead of 10,000 rpm. The temperature was raised to 100 ° C. and held for 120 minutes. Next, stirring was stopped, the solid product was allowed to settle, and the supernatant liquid was siphoned off.
Next, the following operation was repeated twice.
To the solid product was added 250 mL of fresh TiCl ₄ and the mixture was reacted at 120 ° C. for 60 minutes and the supernatant was siphoned off. The solid was washed 6 times with anhydrous hexane at 60 ° C. The anhydrous hexane used for one washing was 100 mL.

(2) Preparation and polymerization of catalyst An autoclave with an internal volume of 3 L equipped with a stirrer was prepared. A stainless steel container (additional device) with an internal volume of 20 cm ³ capable of press-fitting the catalyst into the autoclave was attached to the autoclave, and the interior of the additional device was purged with nitrogen. The inside of the autoclave was purged with nitrogen, and 4.9 mmol of triethylaluminum as component (B) was added while feeding a small amount of nitrogen into the autoclave. After replacing the inside of the autoclave with propylene gas, 0.24 mol% of hydrogen and 16.0 mol of propylene were added and stirred at 25 ° C, and the temperature was raised to 30 ° C. 15 mL of the solid catalyst component hexane slurry of component (A) prepared in (1) (5 mg as a solid catalyst) was placed in a supplementer in a state where a small amount of nitrogen was fed.

  The inside of the adder was pressurized to 4 MPa with nitrogen, and the catalyst was pressed into the autoclave. The autoclave was heated to 80 ° C., and propylene was polymerized for 60 minutes. By adding the component (A) from the adder, the component (A) and the component (B) charged in the autoclave were brought into contact with each other to produce a polymerization catalyst, and also in contact with propylene. That is, τ in this example is 0 seconds. After the polymerization, unreacted propylene was purged to obtain polypropylene. The obtained polypropylene was vacuum-dried at 60 ° C. for 16 hours, and MFR, XI, and polymerization activity were analyzed according to the above method.

  In this example, since the component (A) at room temperature (25 ° C.) and the component (B) present in the 30 ° C. autoclave are brought into contact with each other, the contact temperature during catalyst preparation cannot be measured. However, it is clear that the contact temperature is in the range of 25-30 ° C.

[Example 1-2]
(1) Preparation of solid catalyst component Component (A) was prepared in the same manner as in Example 1-1.

(2) Preparation and polymerization of catalyst An autoclave with an internal volume of 3 L equipped with a stirrer was prepared. The inside of the autoclave was purged with nitrogen, and an adder was attached while feeding a small amount of nitrogen into the autoclave. After replacing the inside of the autoclave with propylene gas, 0.24 mol% of hydrogen and 16.0 mol of propylene were added and stirred at 25 ° C, and the temperature was raised to 30 ° C. 4.9 mmol of triethylaluminum, which is component (B), was placed in a supplementer in a state where a small amount of nitrogen was fed. As a solid catalyst component of component (A) prepared in (1), 5 mg was placed in an adder, and component (B) at 25 ° C. and component (A) at 25 ° C. were contacted.

  Ten seconds after component (A) was added to the adder, the inside of the adder was pressurized to 4 MPa with nitrogen, and the catalyst was pressed into the autoclave. That is, τ in this example was 10 seconds. The autoclave was heated to 80 ° C., and propylene was polymerized for 60 minutes. After the polymerization, unreacted propylene was purged to obtain polypropylene. The obtained polypropylene was vacuum-dried at 60 ° C. for 16 hours, and MFR, XI, and polymerization activity were analyzed according to the above method.

[Example 1-3]
Polypropylene was produced and evaluated in the same manner as in Example 1-2 except that τ was 180 seconds.

[Reference Examples 1-1 and 1-2]
Polypropylene was produced and evaluated in the same manner as in Example 1-2 except that τ was 600 seconds and 1800 seconds, respectively.
[Reference Examples 1-3, 1-4]
Polypropylene was produced and evaluated in the same manner as in Example 1-2 except that τ was 10800 seconds and 2592000 seconds, respectively.

[Examples 2-1 and 2-2]
Polypropylene was produced and evaluated in the same manner as in Examples 1-2 and 1-3 except that component (A) and component (B) were contacted at 15 ° C.

[Reference Examples 2-1 and 2-2]
Polypropylene was produced and evaluated in the same manner as in Example 2 except that τ was 600 seconds and 1800 seconds, respectively.

[Examples 3-1 and 3-2]
Polypropylene was produced and evaluated in the same manner as in Example 2 except that component (A) and component (B) were contacted at 5 ° C.

[Reference Examples 3-1, 3-2]
Polypropylene was produced and evaluated in the same manner as in Example 3 except that τ was 600 seconds and 1800 seconds, respectively.
These results are shown in Table 1 and FIG.

  It is clear that high activity can be achieved when τ is 180 seconds or less. This effect is remarkable when the contact temperatures of the components (A) and (B) are 3 to 30 ° C. Further, when the contact temperature is 3 to 20 ° C., it has a relatively high activity even when τ is 600 seconds or less.

Claims (5)

(A) a solid catalyst containing magnesium, titanium, halogen, and a succinate compound as an internal electron donor compound, and (B) α- using a catalyst containing an organoaluminum compound and no external electron donor compound A method for producing a polymer of olefins, comprising:
Contacting the components (A) and (B) to prepare the catalyst, and contacting the catalyst with α-olefins,
When τ is the time from when the components (A) and (B) are contacted to prepare the catalyst until the catalyst is contacted with the α-olefins, the τ is 180 seconds or less.
The manufacturing method.   The manufacturing method according to claim 1, wherein the τ is 3 to 180 seconds.   The manufacturing method of Claim 1 or 2 whose temperature which makes each component contact in the said catalyst preparation process is 3-30 degreeC.   The manufacturing method of Claim 1 or 2 whose temperature which makes each component contact in the said catalyst preparation process is 3-20 degreeC. A reactor for the production method according to claim 1,
A polymerization reactor, and an introduction device for introducing the catalyst into the reactor,
A reaction apparatus comprising a contact portion for preparing the catalyst by bringing the introduction device into contact with components (A) and (B).