JP2005089580A - Method for improving fluidity of polymer powder - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for improving fluidity of polymer powder, with which fluidity of polymer powder such as polyolefin powder, etc., in an environment field of powder flow is improved, a heat spot hardly occurs in polymerization, excellent fluidity is secured even in dead spaces in piping and various facilities in which polymer powder is moved and neither a polymer lump nor a sheetlike material is formed. <P>SOLUTION: The method for improving fluidity of polymer powder comprises supplying a specific fluidity improver to the environment field of powder flow in a monomer polymerization process or a storage process of the obtained polymer powder. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a method for improving the fluidity of polymer powder, and more particularly, to a method for improving the fluidity of polymer powder such as polyolefin powder in a powder fluid environment.

  Conventionally, as a method for (co) polymerizing monomers and the like, various known methods such as liquid phase polymerization and gas phase polymerization have been used. Among these polymerization methods, (co) polymer is obtained in powder form in gas phase polymerization, and the obtained (co) polymer is collected in powder form for ease of handling in liquid phase polymerization. There are many. The polymer powder is stored in a closed space where the polymer powder exists, for example, a polymerization reactor for producing polymer powder in gas phase polymerization, each pipe, or polymer powder obtained by liquid phase gas phase polymerization or gas phase polymerization. It is required to have excellent fluidity in a storage room or the like.

  By the way, polyolefins such as polyethylene, polypropylene, ethylene / α-olefin copolymer, and propylene / α-olefin copolymer are used in the presence of a solid catalyst such as a solid titanium catalyst or a carrier-supported metallocene catalyst. , Produced by (co) polymerizing olefins. The solid catalyst often has low fluidity, which makes it difficult to supply it to the polymerization vessel.

  In addition, when the olefin is vapor-phase polymerized in the presence of the solid catalyst as described above, a polymer lump or sheet-like material is generated in the fluidized bed, or the fluidity of the polyolefin powder is reduced, and the fluidized bed In some cases, the mixed state becomes non-uniform so that stable operation over a long period of time becomes impossible.

  In addition, pipes attached to the polymerization reactor, pipes connecting the polymerization reactors of each stage when performing gas phase polymerization using a fluidized bed reactor in multiple stages, and other facilities for moving the polymer are connected to the solid catalyst. Alternatively, when the polymer powder moves, the fluidity decreases, or a polymer lump is generated in a place where the fluidity in various facilities decreases, so-called dead space, or the polymer powder adheres to the sheet-like material. In the worst case, there is a problem that the piping is blocked.

  In addition, since the fluidity of the polymer powder is reduced in the storage of the polymer powder finally obtained or stored, the polymer powder is bonded to each other in the storage. There is also a problem that various subsequent processes are delayed, such as the generation of a bridge.

For the purpose of reducing the above problems, a method of adding ethanol to a polymerization vessel has been disclosed. However, ethanol is generally a poisoning substance of an olefin polymerization catalyst, and there is a problem that the catalytic activity is lowered. is there.
JP 2001-261720 A

  The problem to be solved is that, in the process of polymerizing monomers or storing the obtained polymer powder, the fluidity of the polymer powder is reduced, resulting in lumps and the like, and stable operation for a long time cannot be achieved. It is.

  The present invention relates to a monomer polymerization step or a storage step of the obtained polymer powder, wherein the amide represented by (a) (a-1) general formula (I) or (II) is applied to the powder flow environment field. (A-2) supplying at least one compound selected from (a-2) an amine represented by the general formula (III) and (a-3) an ester represented by the general formula (IV); To do.

(In the formula, R ¹ represents a hydrocarbon group having 3 to 40 carbon atoms, and n is 0 to 40.)

(In the formula, R ² and R ³ may be the same or different from each other, and represent a hydrocarbon group having 3 to 40 carbon atoms, and R ⁴ is a divalent hydrocarbon group having 1 to 20 carbon atoms. .)

(In the formula, R ⁵ and R ⁶ may be the same as or different from each other, represent a hydrocarbon group having 3 to 40 carbon atoms, and p + q is 2 to 40.)

(In the formula, R ⁷ represents a hydrocarbon group having 3 to 40 carbon atoms, and m is 1 to 40.)

According to the present invention, the polymer powder has excellent fluidity, heat spots are hardly generated during polymerization, and excellent fluidity can be ensured even in dead spaces in piping and various facilities where the polymer powder moves. And no polymer lump or sheet-like material is produced from the polymerized powder. Further, the supply method has a high degree of freedom and can be supplied by a simple and economical method. Furthermore, since no lump is formed during the gas phase polymerization, it is easy to extract the polymer powder, thereby improving productivity.

  The method for improving the fluidity of the polymer powder according to the present invention will be specifically described below. In the method for improving the fluidity of polymer powder according to the present invention, a powder flow environment field in a production process or storage process of a polymer for (co) polymerizing various monomers, for example, a polymerization reactor and piping attached thereto, multistage polymerization Piping for connecting the polymerization reactors of the apparatus, extraction pot for extracting the obtained polymer powder from the polymerization reactor and piping attached thereto, polymer storage and piping attached thereto, and other polymer powder transportation Selected from the specific (a-1) amide, (a-2) amine, and (a-3) ester represented by the general formulas (I) to (IV) in the closed space where the polymer powder such as piping exists. By supplying at least one kind of compound, the fluidity of the polymer powder in these powder flow environment fields is improved.

  The polymer powder present in the powder flow environment field of the present invention is not particularly limited as long as it is a (co) polymer powder obtained by various known methods such as liquid phase polymerization and gas phase polymerization, For example, the raw (co) polymer powder obtained by gas phase polymerization, or the (co) polymer powder recovered from the liquid phase after being obtained by liquid phase polymerization can be used.

  In the powder flow environment field, it is desirable that the moisture content in the total gas is 2 ppm or less, preferably 0.5 ppm or less or that no moisture is present. If the water content in the total gas exceeds 2 ppm, the polymerization activity tends to decrease remarkably, which is not preferable.

  Further, the compound (a) is present in the powder flow environment field so that it is present in an amount of 0.1 to 400 ppm, preferably 0.5 to 350 ppm, more preferably 1.5 to 300 ppm, based on the weight of the polymer powder. Supplied. When the supply ratio of the compound (a) exceeds the above range, it may be economically disadvantageous, or the polymerization activity may be reduced. is there.

  The compound (a) may be supplied continuously or intermittently to the powder flow environment field, but it is particularly preferable to supply it intermittently. The compound (a) may be supplied to one powder flow environment field or may be supplied to a plurality of powder flow environment fields.

  Next, the compound (a) used in the present invention will be described.

(A-1) Amide The (a-1) amide used in the present invention is represented by the general formula (I) or (II).

In the general formula (I), R ¹ is a hydrocarbon group having 3 to 40 carbon atoms, preferably a hydrocarbon group having 4 to 30 carbon atoms, and more preferably a hydrocarbon group having 5 to 25 carbon atoms. It is a group. Specifically, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, Nonadecyl, eicosyl, heneicosyl, docosyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl And hexadecenyl group, heptadecenyl group, octadecenyl group, nonadecenyl group, eicocenyl group, henecocenyl group, dococenyl group and the like. These examples include isomers. n is 0-40, Preferably it is 0-30, More preferably, it is 0-20.

In the general formula (II), R ² and R ³ may be the same or different from each other, and are a hydrocarbon group having 3 to 40 carbon atoms, preferably a hydrocarbon group having 4 to 30 carbon atoms. More preferably, it is a hydrocarbon group having 5 to 25 carbon atoms. Specific examples thereof include the same hydrocarbon groups as those exemplified for R ¹ above. R ⁴ is a divalent hydrocarbon group having 1 to 20 carbon atoms, preferably a divalent hydrocarbon group having 2 to 10 carbon atoms. Specific examples include an ethylene group, a phenylene group, and a xylylene group. These examples include isomers.

  Specific examples of the amide represented by the general formula (I) include caprylic acid amide, capric acid amide, lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, oleic acid amide, and erucic acid. Examples include amides and polyoxyethylene coconut oil fatty acid monoethanolamide.

  Specific examples of the amide represented by the general formula (II) include ethylene bis stearic acid amide, ethylene bis erucic acid amide, ethylene bis lauric acid amide, ethylene bis stearic acid amide, m-xylene bis stearic acid amide, p- Examples thereof include phenylene bis stearamide.

(A-2) Amine The (a-2) amine used in the present invention is represented by the general formula (III).

In the general formula (III), R ⁵ and R ⁶ may be the same or different from each other, and are a hydrocarbon group having 3 to 40 carbon atoms, preferably a hydrocarbon group having 4 to 30 carbon atoms. More preferably, it is a hydrocarbon group having 5 to 25 carbon atoms. Specific examples thereof include the same hydrocarbon groups as those exemplified for R ¹ above. p + q is 2-40, preferably 2-30, more preferably 2-20.

  Specific examples of the amine represented by the general formula (III) include polyoxyethylene laurylamine capryl ester and stearyl diethanolamine monostearate.

(A-3) Ester The (a-3) ester used in the present invention is represented by the general formula (IV).

In the general formula (IV), R ⁷ is a hydrocarbon group having 3 to 40 carbon atoms, preferably a hydrocarbon group having 4 to 30 carbon atoms, and more preferably a hydrocarbon group having 5 to 25 carbon atoms. It is a group. Specific examples thereof include the same hydrocarbon groups as those exemplified for R ¹ above. m is 1-40, Preferably it is 1-30, More preferably, it is 1-20.

  Specific examples of the ester represented by the general formula (IV) include polyethylene glycol monolaurate, polyethylene glycol monostearate, and polyethylene glycol monooleate.

  The above (a-1) amide, (a-2) amine, and (a-3) ester can be used singly or in combination of two or more.

  The flowability improving method of the polymer powder according to the present invention is particularly preferably applied when the powder flow environment field is a polymerization reactor of an olefin gas phase continuous polymerization apparatus and the polymer powder is a polyolefin powder. .

  Examples of the polyolefin powder include α-olefins having 2 to 20 carbon atoms, such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene; cyclic olefins having 3 to 20 carbon atoms, such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, Powder of at least one (co) polymer selected from olefins such as 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene Is mentioned.

  Among these, the method for improving the fluidity of the polymer powder according to the present invention is to improve the fluidity of the ethylene homopolymer powder or the copolymer powder of ethylene and an α-olefin having 3 to 8 carbon atoms. It is suitable for.

  As a method for (co) polymerizing olefins using a gas phase continuous polymerization apparatus, using a solid catalyst as described later, for example, using a gas phase fluidized bed reactor as shown in FIG. There is a way to polymerize. FIG. 1 shows a schematic diagram of an example of a gas phase fluidized bed reactor.

  When (co) polymerizing olefins using a gas phase fluidized bed reactor, the solid catalyst is supplied to the fluidized bed reactor 3 in the form of a solid powder via the catalyst supply line 1, for example. Gaseous olefins and the like are continuously supplied from, for example, the supply gas line 7 and are supplied from below the fluidized bed reactor 3 through the gas distribution plate 4 such as a perforated plate through the circulation gas line 6 by a circulation gas blower (not shown). And blown. Thereby, the fluidized bed (reaction system) 5 is maintained in a fluidized state. The olefin blown into the fluidized bed 5 in which such a solid catalyst is maintained in a fluidized state undergoes a polymerization reaction to produce a polymerized powder (polyolefin powder). The produced polyolefin powder is continuously withdrawn from the fluidized bed reactor 3 through the polymer discharge line 8. Unreacted gaseous olefin or the like that has passed through the fluidized bed 5 is decelerated in a deceleration zone 3a provided above the fluidized bed reactor 3 and discharged from the exhaust gas line 2 to the outside of the fluidized bed reactor 3, and is not shown. In the heat exchanger, the heat of polymerization is removed and the refrigerant is circulated from the circulation gas line 6 to the fluidized bed 5 again. Molecular weight regulators such as hydrogen can be supplied from any location in the gas phase fluidized bed reactor, for example from the feed gas line 7.

  When the present invention is applied to an olefin polymerization process using such a gas phase fluidized bed reactor, at least one compound selected from the compound (a) is present at any location in the gas phase fluidized bed reactor. Can be supplied to, for example, a fluidized bed reactor, a supply gas line, a circulation gas line, and an exhaust gas line.

  In the present invention, when the compound (a) is supplied to the gas phase fluidized bed reactor, it is continuously or intermittently introduced into the fluidized bed reactor 3 from the bottom of the dispersion plate 4 via the circulating gas line 6. It is preferable to supply or continuously or intermittently supply into the fluidized bed reactor 3 from above the dispersion plate 4, and in any case, it is more preferable to supply intermittently.

  Thus, if the said compound (a) is supplied to a fluid environment field, sufficient effect will be acquired even if the quantity of the compound (a) to be used is small, and it can add very efficiently. Moreover, the quantitative quantity of the addition amount is good, and it becomes possible to add very quantitatively.

  Furthermore, it can be added at any time while confirming the state of the fluid environment, and it is possible to instantly determine the influence on the polymerization state such as a decrease in catalyst activity due to the addition of the compound (a). Further, it is possible to suppress the catalyst activity to a minimum or to minimize the influence on the physical properties of the obtained polyolefin powder.

  As the solid catalyst used in the gas phase continuous polymerization apparatus, specifically, a carrier-supporting type in which a transition metal compound selected from Group 3 to Group 12 of the periodic table and an organoaluminum oxy compound are supported on a particulate carrier. Transition metal compound catalyst, solid titanium catalyst composed of a solid titanium catalyst component and an organoaluminum compound, so-called an inorganic oxide solid such as silica supporting an arbitrary chromium compound that can be oxidized to chromium trioxide. Among them, a carrier-supported transition metal compound-based catalyst is preferable, and a transition metal metallocene compound selected from Group 4 of the periodic table and an organoaluminum oxy compound are supported on a particulate carrier. A carrier-supported metallocene catalyst is preferred.

  The carrier-supported metallocene catalyst is formed from (A) a transition metal compound of Group 4 of the periodic table having a cyclopentadienyl skeleton, (B) an organoaluminum oxy compound, and (C) a particulate carrier. Yes.

  The carrier-supported metallocene catalyst may be prepolymerized. Such a prepolymerized carrier-supported metallocene catalyst (hereinafter referred to as “preliminarily polymerized metallocene catalyst”) is (A). Formed from a transition metal compound of Group 4 of the periodic table having a cyclopentadienyl skeleton, (B) an organoaluminum oxy compound, (C) a particulate carrier, and (D) an olefin polymer produced by prepolymerization. Has been.

Hereinafter, each component which forms the solid polymerization catalyst for olefin polymerization and the prepolymerization catalyst for olefin polymerization according to the present invention will be described first.
(A) Transition metal compound (A) Examples of the transition metal compound of Group 4 of the periodic table having a cyclopentadienyl skeleton include compounds represented by the following general formula (V).

  In the formula, M is a transition metal of Group 4 of the periodic table, specifically, zirconium, titanium, or hafnium.

L is a ligand (group) coordinated to a transition metal, and at least one L is a ligand having a cyclopentadienyl skeleton, other than a ligand having a cyclopentadienyl skeleton. L is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a halogen atom, a trialkylsilyl group, or —SO ₃ R (where R is a carbon which may have a substituent such as halogen). Or a hydrogen atom.

  x is the valence of the transition metal and represents the number of L. Examples of the ligand having a cyclopentadienyl skeleton include cyclopentadienyl group; methylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group, penta Methylcyclopentadienyl group, ethylcyclopentadienyl group, methylethylcyclopentadienyl group, propylcyclopentadienyl group, methylpropylcyclopentadienyl group, butylcyclopentadienyl group, methylbutylcyclopentadienyl Examples thereof include alkyl-substituted cyclopentadienyl groups such as hexylcyclopentadienyl group; indenyl group; 4,5,6,7-tetrahydroindenyl group; fluorenyl group and hydrocarbon substituents thereof. These groups may be substituted with a halogen atom, a trialkylsilyl group or the like.

  Among the ligands coordinated to these transition metals, an alkyl-substituted cyclopentadienyl group is particularly preferable. When the compound represented by the general formula (V) includes two or more groups having a cyclopentadienyl skeleton, the group having two cyclopentadienyl skeletons is an alkylene group such as ethylene or propylene; It may be bonded via an alkylidene group such as isopropylidene or diphenylmethylene; a silylene group; a substituted silylene group such as a dimethylsilylene group, a diphenylsilylene group or a methylphenylsilylene group. Further, the groups having two or more cyclopentadienyl skeletons are preferably the same.

  Examples of the ligand other than the ligand having a cyclopentadienyl skeleton include the following. Specific examples of the hydrocarbon group having 1 to 12 carbon atoms include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group and pentyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; phenyl And aryl groups such as a tolyl group and aralkyl groups such as a benzyl group and a neophyll group.

  Examples of the alkoxy group include a methoxy group, an ethoxy group, and a butoxy group. Examples of the aryloxy group include a phenoxy group.

Examples of halogen include fluorine, chlorine, bromine and iodine. Examples of the ligand represented by —SO ₃ R include a p-toluenesulfonate group, a methanesulfonate group, a trifluoromethanesulfonate group, and the like.

For example, when the valence of the transition metal is 4, the compound represented by the general formula (V) is more specifically represented by the following general formula (V-1).
R ¹¹ R ¹² R ¹³ R ¹⁴ M ----- (V-1)
(Wherein, M is zirconium, titanium or hafnium, R ¹¹ is a group having a cyclopentadienyl skeleton, and R ¹² , R ¹³ and R ¹⁴ may be the same or different from each other, A group having a pentadienyl skeleton, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a halogen atom, a trialkylsilyl group, —SO ₃ R, or a hydrogen atom.)
In the present invention, a transition metal compound in which one of R ¹² , R ¹³ and R ^{14 in} the general formula (V-1) is a group having a cyclopentadienyl skeleton, for example, R ¹¹ and R ¹² are cyclopentadienyl. A transition metal compound which is a group having a skeleton is preferably used. In this case, these groups having a cyclopentadienyl skeleton may be bonded via an alkylene group, a substituted alkylene group, an alkylidene group, a silylene group, a substituted silylene group, or the like. R ¹³ and R ¹⁴ are an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a halogen atom, a trialkylsilyl group, —SO ₃ R, or a hydrogen atom.

  Below, a specific compound is illustrated about the transition metal compound whose M is a zirconium. Bis (indenyl) zirconium dichloride, bis (indenyl) zirconium dibromide, bis (indenyl) zirconium bis (p-toluenesulfonate), bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, bis (fluorenyl) Zirconium dichloride, ethylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dibromide, ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) diphenylzirconium, ethylenebis (indenyl) methylzirconium monochloride, ethylenebis (indenyl) ) Zirconium bis (methanesulfonate), ethylenebis (indenyl) zirconium bis (p-toluenesulfonate), ethylenebis (i Denyl) zirconium bis (trifluoromethanesulfonate), ethylene bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl- Methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (cyclopentadienyl) zirconium dichloride, dimethylsilylenebis (methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (Trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride, dimethyl Lucylylene bis (indenyl) zirconium bis (trifluoromethanesulfonate), rac-dimethylsilylene bis {1- (2-methyl-4,5-acenaphthocyclopentadienyl)} zirconium dichloride, rac-dimethylsilylene bis {1- ( 2-methyl-4,5-benzoindenyl)} zirconium dichloride, rac-dimethylsilylenebis {1- (2-methyl-4-isopropyl-7-methylindenyl)} zirconium dichloride, rac-dimethylsilylenebis {1 -(2-Methyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylenebis {1- (2-methylindenyl)} zirconium dichloride, dimethylsilylenebis (4,5,6,7-tetrahydroindenyl) ) Zirconium Loride, dimethylsilylene (cyclopentadienyl-fluorenyl) zirconium dichloride, diphenylsilylene bis (indenyl) zirconium dichloride, methylphenylsilylene bis (indenyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) ) Zirconium dibromide, bis (cyclopentadienyl) methyl zirconium monochloride, bis (cyclopentadienyl) ethyl zirconium monochloride, bis (cyclopentadienyl) cyclohexyl zirconium monochloride, bis (cyclopentadienyl) phenyl zirconium Monochloride, bis (cyclopentadienyl) benzylzirconium monochloride, bis (cyclopentadienyl) zirconium Nochloride monohydride, bis (cyclopentadienyl) methylzirconium monohydride, bis (cyclopentadienyl) dimethylzirconium, bis (cyclopentadienyl) diphenylzirconium, bis (cyclopentadienyl) dibenzylzirconium, bis ( Cyclopentadienyl) zirconium methoxychloride, bis (cyclopentadienyl) zirconium ethoxy chloride, bis (cyclopentadienyl) zirconium bis (methanesulfonate), bis (cyclopentadienyl) zirconium bis (p-toluenesulfonate) ), Bis (cyclopentadienyl) zirconium bis (trifluoromethanesulfonate), bis (methylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadiene) Nyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium ethoxy chloride, bis (dimethylcyclopentadienyl) zirconium bis (trifluoromethanesulfonate), bis (ethylcyclopentadienyl) zirconium dichloride, bis (1,3 -Ethylmethylcyclopentadienyl) zirconium dichloride, bis (propylcyclopentadienyl) zirconium dichloride, bis (1,3-methylpropylcyclopentadienyl) zirconium dichloride, bis (butylcyclopentadienyl) zirconium dichloride, bis (1,3-butylmethylcyclopentadienyl) zirconium dichloride, bis (1,3-butylmethylcyclopentadienyl) zirconium bis (methanesulfonate), bis (Trimethylcyclopentadienyl) zirconium dichloride, bis (tetramethylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (hexylcyclopentadienyl) zirconium dichloride, bis (trimethylsilylcyclopenta) Dienyl) zirconium dichloride and the like.

  In the above examples, the disubstituted product of the cyclopentadienyl ring includes 1,2- and 1,3-substituted products, and the trisubstituted product includes 1,2,3- and 1,2,4-substituted products. Including. Alkyl groups such as propyl and butyl include isomers such as n-, i-, sec- and tert-.

  In the present invention, a transition metal compound in which zirconium metal is replaced with titanium metal or hafnium metal in the above-described zirconium compound can also be used.

(B) Organoaluminum oxy compound (B) The organoaluminum oxy compound may be a conventionally known aluminoxane, or a benzene-insoluble organoaluminum as disclosed in JP-A-2-276807. It may be an oxy compound.

  A conventionally well-known aluminoxane can be manufactured by the following methods, for example.

  (1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, first cerium chloride hydrate, etc. A method of reacting an organoaluminum compound with adsorbed water or crystal water by adding an organoaluminum compound such as trialkylaluminum to the hydrocarbon medium suspension.

  (2) A method of allowing water, ice or water vapor to act directly on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran.

  (3) A method in which an organotin oxide such as dimethyltin oxide or dibutyltin oxide is reacted with an organoaluminum compound such as trialkylaluminum in a medium such as decane, benzene, or toluene.

  In addition, this aluminoxane may contain a small amount of organometallic components. Further, after removing the solvent or the unreacted organoaluminum compound by distillation from the recovered solution of the above aluminoxane, it may be redissolved in the solvent.

  Specific examples of the organoaluminum compound used in preparing the aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert- Trialkylaluminum such as butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum; tricycloalkylaluminum such as tricyclohexylaluminum, tricyclooctylaluminum; dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide Diisobutylaluminum chloride Le Kill halides diethyl aluminum hydride, dialkylaluminum hydride such as diisobutylaluminum hydride; dimethyl aluminum methoxide, dialkylaluminum alkoxides such as diethylaluminum ethoxide; and dialkylaluminum Ally Loki Sid such as diethyl aluminum phenoxide and the like.

Of these, trialkylaluminum and tricycloalkylaluminum are particularly preferred. Further, as the organoaluminum compound represented by the following general formula _{(i-C 4 H 9)} x Al y (C 5 H 10) z
Isoprenyl aluminum represented by (x, y, z is a positive number and z ≧ 2x) can also be used.

  The above organoaluminum compounds are used alone or in combination. Solvents used in the preparation of aluminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane, Cycloaliphatic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane and methylcyclopentane, petroleum fractions such as gasoline, kerosene and light oil or halides of the above aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons, among others , Hydrocarbon solvents such as chlorinated products and brominated products. In addition, ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons are particularly preferred.

(C) Particulate carrier (C) Specifically, the particulate carrier may be SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO _2, etc. Mixtures containing these, such as SiO ₂ —MgO, SiO ₂ —Al ₂ O ₃ , SiO ₂ —TiO ₂ , SiO ₂ —V ₂ O ₅ , SiO ₂ —Cr ₂ O ₃ , SiO ₂ —TiO ₂ —MgO, etc. Mention may be made of inorganic carriers or organic carriers such as polyethylene, polypropylene, poly 1-butene, poly 4-methyl-1-pentene, styrene-divinylbenzene copolymer.

  Such (C) particulate carrier preferably has an average particle diameter in the range of 1 to 300 μm, preferably 10 to 200 μm. The carrier-supported metallocene catalyst preferably used in the present invention includes (A) the transition metal compound of Group 4 of the periodic table having a cyclopentadienyl skeleton, (B) the organoaluminum oxy compound, and (C ) A particulate carrier is contained as an essential component, but (E) an organoaluminum compound may be contained as necessary.

As such (E) organoaluminum compound, for example, an organoaluminum compound represented by the following general formula (VI) can be exemplified.
R ^a _n AlX _3-n ------ (VI)
(In the formula, Ra represents ^a hydrocarbon group having 1 to 12 carbon atoms, X represents a halogen atom or a hydrogen atom, and n is 1 to 3).
In the general formula (VI), R ^a is a hydrocarbon group having 1 to 12 carbon atoms, such as an alkyl group, a cycloalkyl group, or an aryl group. Specifically, a methyl group, an ethyl group, n- Examples thereof include propyl group, isopropyl group, isobutyl group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group, and tolyl group.

  Specific examples of such an organoaluminum compound (E) include the following compounds. Trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri-2-ethylhexylaluminum; alkenylaluminum such as isoprenylaluminum; dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutyl Dialkylaluminum halides such as aluminum chloride and dimethylaluminum bromide; alkylaluminum sesquichlorides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride and ethylaluminum sesquibromide; Le aluminum dichloride, ethyl aluminum dichloride, alkyl aluminum dihalides such as isopropyl aluminum dichloride, ethyl aluminum dibromide; diethylaluminum hydride, and alkyl aluminum hydride such as diisobutyl aluminum hydride.

Moreover, the compound represented by the following general formula (VII) can also be used as the organoaluminum compound (E).
R ^a _n AlY _3-n ----- (VII)
(In the formula, R ^a is the same as above, and Y is —OR ^b group, —OSiR ^c ₃ group, —OAlR ^d ₂ group, —NR ^e ₂ group, —SiR ^f ₃ group or —N (R ^g ). AlR ^h ₂ group, n is 1 to 2, R ^b , R ^c , R ^d and R ^h are methyl group, ethyl group, isopropyl group, isobutyl group, cyclohexyl group, phenyl group, etc., and R ^e Is a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, a phenyl group, a trimethylsilyl group, etc., and R ^f and R ^g are a methyl group, an ethyl group, etc.)
Specific examples of such an organoaluminum compound include the following compounds.
_{^{(1) R a n Al (}} OR b) a compound represented by _3-n, e.g., dimethylaluminum methoxide, diethylaluminum ethoxide and diisobutylaluminum methoxide,
_{^{(2) R a n Al (}} OSiR c 3) a compound represented by _3-n, e.g., _{Et 2 Al (OSiMe 3),} (iso-Bu) 2 Al (OSiMe 3), (iso-Bu) 2 Al ( OSiEt ₃ ) etc .;
_{^{(3) R a n Al (}} OAlR d 2) a compound represented by _3-n, e.g., _{Et 2} AlOAlEt 2, such as _{(iso-Bu) 2 AlOAl (} iso-Bu) 2;
_{^{(4) R a n Al (}} NR e 2) a compound represented by _3-n, e.g., _{Me 2 AlNEt 2, Et 2 AlNHMe} , Me 2 AlNHEt, Et 2 AlN (SiMe 3) 2, (iso-Bu) 2 AlN (SiMe ₃ ) ₂ etc .;
_{^{(5) R a n Al (}} SiR f 3) a compound represented by _3-n, such as _{(iso-Bu) 2 AlSiMe 3} ;
_{^{(6) R a n Al (}} N (R g) AlR h 2) 3-n compound represented by, for example, _{Et 2 AlN (Me) AlEt 2} , (iso-Bu) 2 AlN (Et) Al (iso- Bu) ₂ etc.
Among the organoaluminum compounds represented by the general formula (VI) or (VII), the general formula _{^{R a 3 Al, R a n}} Al (OR b) 3-n, R a n Al (OAlR d 2) 3 A compound represented by _-n is preferable, and a compound in which ^Ra is an isoalkyl group and n = 2 is particularly preferable.

Carrier-supported metallocene catalyst The carrier-supported metallocene catalyst preferably used in the present invention comprises (A) the transition metal compound of Group 4 of the periodic table having a cyclopentadienyl skeleton, and (B) organoaluminum oxy. It is formed from a compound, the (C) fine particle carrier, and, if necessary, the (E) organoaluminum compound.

  Such a carrier-supported metallocene catalyst includes (A) a transition metal compound belonging to Group 4 of the periodic table having a cyclopentadienyl skeleton, (B) an organoaluminum oxy compound, (C) a particulate carrier, and According to (E), it can be prepared by bringing the organoaluminum compound into mixed contact. The contact order of each component is arbitrarily selected.

  Specific examples of the inert hydrocarbon solvent used for the preparation of the carrier-supported metallocene catalyst include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane And alicyclic hydrocarbons such as methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, and mixtures thereof.

  In preparing the carrier-supported metallocene catalyst, (A) the transition metal compound is usually 0.001 to 1.0 mmol, preferably 0.005 to 0, in terms of transition metal atom, per gram of (C) particulate carrier. The (B) organoaluminum oxy compound is usually used in an amount of 0.1 to 100 mmol, preferably 0.5 to 20 mmol in terms of aluminum atom.

  When (E) an organoaluminum compound is used, it is usually used in an amount of 0.001 to 1000 mmol, preferably 2 to 500 mmol, per 1 g of (C) particulate carrier.

  The temperature at which the above components are mixed and contacted is usually −50 to 150 ° C., preferably −20 to 120 ° C., and the contact time is 1 to 1000 minutes, preferably 5 to 600 minutes.

The carrier-supported metallocene catalyst thus obtained is about 5 × 10 ⁻⁶ to 10 ⁻³ mol, preferably 10 ×, of (A) transition metal compound in terms of transition metal atom per 1 g of (C) fine particle support. Supported in an amount of ^{-5 to} 3 × 10 ⁻⁴ mol, and (B) an organoaluminum oxy compound (including (A) an organoaluminum compound, if necessary, including its aluminum) is about an aluminum atom equivalent. It is desired to be supported in an amount of 10 ⁻³ to 10 ⁻¹ mol, preferably 2 × 10 ^{−3 to} 5 × 10 ⁻² mol.

Prepolymerized metallocene-based catalyst The prepolymerized catalyst comprises (A) a transition metal compound, (B) an organoaluminum oxy compound, (C) a particulate carrier, and (E) an organoaluminum compound as necessary. And (D) an olefin polymer produced by preliminary polymerization.

  As a method for preparing such a prepolymerization catalyst, for example, (A) a transition metal compound, (B) an organoaluminum oxy compound, and (C) a particulate carrier are contained in an inert hydrocarbon solvent or an olefin medium. There is a method in which a small amount of olefin is prepolymerized to a solid catalyst component obtained by mixing contact.

  In addition, (E) organoaluminum compound can be used at the time of prepolymerization. Examples of the inert hydrocarbon solvent used for the preparation of the prepolymerization catalyst include the same inert hydrocarbon solvents used for preparing the carrier-supported metallocene catalyst.

  The olefin used in the prepolymerization is 100 to 0 mol% of ethylene, 0 to 49 mol% of propylene, and 0 to 100 mol% of olefin having 4 or more carbon atoms, preferably 100 to 0 mol% of ethylene. , 0 to 20 mol% of propylene and 0 to 100 mol% of an olefin having 4 or more carbon atoms, more preferably 100 to 20 mol% of ethylene, 0 to 20 mol% of propylene and 4 carbon atoms. It is desirable to contain the above olefin in the range of 0 to 80 mol%, particularly preferably 100 to 20 mol% of ethylene and the olefin having 4 or more carbon atoms in the range of 0 to 80 mol%.

  Specific examples of the olefin having 4 or more carbon atoms include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, Examples include α-olefins having 4 to 20 carbon atoms, such as 1-hexadecene, 1-octadecene, and 1-eicocene.

  Furthermore, cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a- Octahydronaphthalene, styrene, vinylcyclohexane, dienes and the like can also be used.

  In preparing the prepolymerization catalyst, (A) the transition metal compound is usually 0.001 to 1.0 mmol, preferably 0.005 to 0.5 mmol, per 1 g of (C) particulate carrier, in terms of transition metal atoms. The (B) organoaluminum oxy compound is usually used in an amount of 0.1 to 100 mmol, preferably 0.5 to 20 mmol, in terms of aluminum atom. When (E) an organoaluminum compound is used, it is usually used in an amount of 0.001 to 1000 mmol, preferably 0.01 to 500 mmol, per 1 g of (C) particulate carrier.

The prepolymerization catalyst obtained as described above is about 5 × 10 ⁻⁶ to 10 ⁻³ mol, preferably 10 ⁻ , of (A) transition metal compound in terms of transition metal atom per 1 g of (C) particulate carrier. It is supported in an amount of ^{5 to} 3 × 10 ⁻⁴ mol, and (B) the organoaluminum oxy compound is about 10 ⁻³ to 10 ⁻¹ mol, preferably 2 × 10 ^{−3 to} 5 × 10 ⁻² mol in terms of aluminum atom. It is desirable that the olefin polymer (D) produced by the prepolymerization is carried in an amount of about 0.1 to 500 g, preferably 0.3 to 300 g, particularly preferably 1 to 100 g. .

  The olefin polymerization catalyst used in the present invention can contain other components useful for polymerization in addition to the above components. The olefin polymerization catalyst used in the present invention can polymerize olefins with excellent polymerization activity.

Polymerization of olefins using a polymerization carrier-supported metallocene catalyst and a prepolymerized metallocene catalyst is usually carried out by gas phase polymerization. In the polymerization, (C) an organoaluminum oxy compound and / or (E) an organoaluminum compound not supported on a fine particle carrier can be used.

  When carrying out the gas phase polymerization, the polymerization temperature of the olefin is usually 0 to 120 ° C., preferably 20 to 100 ° C. The polymerization pressure is usually under normal pressure to 10 MPa, preferably normal pressure to 5 MPa, and the polymerization reaction can be carried out in any of batch, semi-continuous and continuous methods.

  The olefin used at the time of polymerization is 100 to 0 mol% ethylene, 0 to 49 mol% propylene and 0 to 100 mol% olefin having 4 or more carbon atoms, preferably 100 to 0 mol% ethylene. 0 to 20 mol% of propylene and an olefin having 4 or more carbon atoms in the range of 0 to 100 mol%, more preferably 100 to 20 mol% of ethylene, 0 to 20 mol% of propylene and 4 or more of carbon atoms It is desirable that the olefin is contained in the range of 0 to 80 mol%, particularly preferably 100 to 20 mol% of ethylene and the olefin having 4 or more carbon atoms in the range of 0 to 80 mol%.

  Specific examples of the olefin having 4 or more carbon atoms include the same olefins having 4 or more carbon atoms used in the prepolymerization.

  In the gas phase polymerization of olefins using a carrier-supported metallocene catalyst and a prepolymerized metallocene catalyst, the addition of the compound (a) to the powder flow environment field in the above-described proportion improves the fluidity of the polymer powder. The polymer lump is not formed or the piping or the like is not clogged, and there is almost no influence on the physical activity of the polyolefin powder obtained by reducing the catalytic activity.

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.

Preparation of solid catalyst component (c1) 10 kg of silica dried at 250 ° C. for 10 hours was suspended in 154 liters of toluene, and then cooled to 0 ° C. Thereafter, 50.5 liters of a toluene solution of methylaminoxan (Al = 1.52 mol / liter) was added dropwise to the suspension over 1 hour. At this time, the temperature in the system was kept in the range of 0 to 5 ° C. Subsequently, the mixture was reacted at 0 ° C. for 30 minutes, then heated to 95 ° C. over 1.5 hours and reacted at that temperature for 4 hours. Thereafter, the temperature was lowered to 60 ° C., and the supernatant was removed by a decantation method. The solid component thus obtained was washed twice with toluene and then resuspended in 100 liters of toluene to make a total volume of 160 liters.

  To the suspension thus obtained, 22.0 liters of a toluene solution of bis (1,3-n-butylmethylcyclopentadienyl) zirconium dichloride (Zr = 25.7 mmol / liter) was added at 80 ° C. The solution was added dropwise over 30 minutes and further reacted at 80 ° C. for 2 hours. Thereafter, the supernatant was removed and washed twice with hexane to obtain a solid catalyst component (c1) containing 3.2 mg of zirconium per 1 g of the solid catalyst component.

Preparation of Prepolymerization Catalyst (c2) A 350 liter reactor sufficiently purged with nitrogen was charged with 7.0 kg of the solid catalyst component (c1) prepared above and hexane to make the total volume 285 liters. After cooling the system to 10 ° C., ethylene was blown into hexane at a flow rate of 8 Nm ³ / hr for 5 minutes. During this time, the temperature in the system was maintained at 10 to 15 ° C. Thereafter, the ethylene supply was stopped, and 2.4 mol of triisobutylaluminum and 1.2 kg of 1-hexene were charged. After the inside of the system was closed, ethylene supply was started again at a flow rate of 8 Nm ³ / hr. After 15 minutes, the flow rate of ethylene was lowered to 2 Nm ³ / hr, and the pressure in the system was adjusted to 0.08 MPaG. During this time, the temperature in the system rose to 35 ° C. Thereafter, ethylene was supplied at a flow rate of 4 Nm ³ / hr for 3.5 hours while adjusting the temperature in the system to 32 to 35 ° C. During this time, the pressure in the system was maintained at 0.07 to 0.08 MPaG. Next, after the inside of the system was replaced with nitrogen, the supernatant was removed and washed twice with hexane. Thus, a prepolymerized catalyst (c2) in which 3 g of polymer was prepolymerized per 1 g of the solid catalyst component was obtained. This prepolymerized polymer had an intrinsic viscosity [η] of 2.1 dl / g and a 1-hexene content of 4.8% by weight.

Copolymerization of ethylene and 1-hexene was performed using a polymerization gas phase fluidized bed polymerization apparatus. The polymerization pressure was 2 MPaG, the polymerization temperature was 80 ° C., and the ethylene composition in the polymerization reactor was 57 mol%. The prepolymerized catalyst (c2) prepared above was fed into the polymerization reactor at 62 g / hr. In the circulating gas line, erucic acid amide (trade name: Alfro P-10, manufactured by NOF Corporation) was intermittently supplied so as to be present in an amount of 30 ppm relative to the weight of the polymer. As the olefin, ethylene was 73 Nm ³ / hr, 1-hexene was 12 liters / hr, and the supply amount was constant, and a polymer was produced at a rate of 80 kg / hr. At this time, the polymer density was 922 kg / m ³ and the melt flow rate was 3.9 g / 10 min. The melt flow rate was measured under conditions of 190 ° C. and 2.16 kg load according to ASTM D1238-65T.

  Although the operation was carried out for 16 hours under these conditions, no heat spots were observed in all locations such as the polymerization vessel and piping, and stable polymerization could be carried out.

[Comparative Example 1]
A polymer was produced at a rate of 80 kg / hr in the same manner as in Example 1 except that the supply amount of the prepolymerized catalyst (c2) was 57 g / hr and Alflow P-10 was not supplied. As a result of operating under these conditions, a heat spot was generated in the polymerization reactor and the like, and the operation could not be continued in 4 hours.

  Example 1 except that polyoxyethylene coconut oil fatty acid monoethanolamide (trade name: Adekasol YA-6, manufactured by Asahi Denka) was intermittently supplied in an amount of 50 ppm instead of erucic acid amide Then, ethylene and 1-hexene were copolymerized. A polymer was produced at a rate of 78 kg / hr. Although the operation was carried out for 16 hours under these conditions, no heat spots were observed in all locations such as the polymerization vessel and piping, and stable polymerization could be carried out.

  In the same manner as in Example 1, except that polyoxyethylene laurylamine capryl ester (trade name: Electrostripper EA7, manufactured by Kao) was supplied intermittently so as to be present in an amount of 30 ppm instead of erucic acid amide. Copolymerization with 1-hexene was performed. A polymer was produced at a rate of 80 kg / hr. Although the operation was carried out for 16 hours under these conditions, no heat spots were observed in all locations such as the polymerization vessel and piping, and stable polymerization could be carried out.

  Ethylene glycol monostearate (trade name: Nonion S-2, manufactured by NOF Corporation) was used instead of erucic acid amide in the same manner as in Example 1 except that it was intermittently supplied so as to be present in an amount of 60 ppm. Copolymerization with 1-hexene was performed. A polymer was produced at a rate of 79 kg / hr. Although the operation was carried out for 16 hours under these conditions, no heat spots were observed in all locations such as the polymerization vessel and piping, and stable polymerization could be carried out.

  Since excellent fluidity can be ensured in the monomer polymerization step and the obtained polymer powder storage step, no polymer mass or sheet-like material is produced. For this reason, long-term stable operation is possible, and it can be applied to means for improving productivity.

It is the schematic which shows an example of a gaseous-phase fluidized bed polymerization apparatus.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Catalyst supply line 2 Exhaust gas line 3 Fluidized bed reactor 4 Gas dispersion plate 5 Fluidized bed 6 Circulating gas line 7 Supply gas line 8 Polymer discharge line

Claims (1)

A monomer polymerization step or a storage step of the obtained polymer powder, wherein (a) (a-1) an amide represented by the general formula (I) or (II), (a- 2) Flowability of polymer powder characterized by supplying at least one compound selected from amine represented by general formula (III) and (a-3) ester represented by general formula (IV) Improvement method.

(In the formula, R ¹ represents a hydrocarbon group having 3 to 40 carbon atoms, and n is 0 to 40.)

(In the formula, R ² and R ³ may be the same or different from each other, and represent a hydrocarbon group having 3 to 40 carbon atoms, and R ⁴ is a divalent hydrocarbon group having 1 to 20 carbon atoms. .)

(In the formula, R ⁵ and R ⁶ may be the same as or different from each other, represent a hydrocarbon group having 3 to 40 carbon atoms, and p + q is 2 to 40.)

(In the formula, R ⁷ represents a hydrocarbon group having 3 to 40 carbon atoms, and m is 1 to 40.)

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