JP3670163B2 - Olefin slurry polymerization method - Google Patents

Description

即ち、重合容器にヘプタンを装入し、系内をエチレンで置換した後、ヘキセンー１と重合触媒（（１）−１とする）を装入し、約１０分間保持した。その後、再び重合触媒（（１）−２とする）を装入し、化合物（Ｂ）を添加した。系内をエチレンで加圧し、昇温して重合を行った。通常の重合は、スカベンジャーとして、上図で触媒（１）−１のところでトリイソブチルアルミニウムなどのアルキルアルミニウムを使用するが、アルキルアルミニウム自身が帯電防止剤としても働くため、化合物（Ｂ）（帯電防止剤）の評価ができない。そこで、本実施例では、アルキルアルミニウムの代わりに、触媒（１）をスカベンジャーとして使用している。上図で触媒（１）−１を使用しなければ、ポリマー収量は極端に少なくなる。触媒（１）−２の一部活性点が系中の不純物で失活するため、上図で触媒（１）−２を使用しなければ、ポリマーはほとんど得られない。触媒（１）−１に含まれるアルミニウム（アルミノキサン由来）のほとんどすべてがスカベンジャーとして働き、触媒（１）−１の活性点のほとんどが失活するためである。
【００７５】
（実施例１）
固体触媒成分（ａ）の調製
２５０℃で１０時間乾燥したシリカ１０ｋｇを、１５４リットルのトルエンに懸濁した後、０℃まで冷却した。その後、この懸濁液に、メチルアミノキサンのトルエン溶液（Ａｌ＝１．５２モル／リットル）５０．５リットルを１時間かけて滴下した。この際、系内の温度を０〜５℃の範囲に保った。引続き０℃で３０分間反応させ、次いで１．５時間かけて９５℃まで昇温し、その温度で４時間反応させた。その後６０℃まで降温し、上澄液をデカンテーション法により除去した。このようにして得られた固体成分をトルエンで２回洗浄した後、トルエン１００リットルで再懸濁し、全量を１６０リットルとした。
【００７６】
このようにして得られた懸濁液に、ビス（1,3-n-ブチルメチルシクロペンタジエニル）ジルコニウムジクロリドのトルエン溶液（Ｚｒ＝２５．７ミリモル／リットル）２２．０リットルを８０℃で３０分間かけて滴下し、さらに８０℃で２時間反応させた。その後、上澄液を除去し、ヘキサンで２回洗浄することにより、固体触媒成分１ｇ当り３．２ｍｇのジルコニウムを含有する固体触媒成分（ａ）を得た。
【００７７】
予備重合触媒（ｂ）の調製
充分に窒素置換した３５０リットルの反応器に、上記で調製した固体触媒成分７．０ｋｇとヘキサンを装入し、全容積を２８５リットルにした。系内を１０℃まで冷却した後、エチレンを８Ｎｍ³／ｈの流量で５分間ヘキサン中に吹き込んだ。この間、系内の温度は、１０〜１５℃に保持した。その後、エチレンの供給を停止し、トリイソブチルアルミニウムを２．４モルおよび1-ヘキセンを１．２ｋｇ装入した。系内を密閉系にした後、８Ｎｍ³／ｈの流量でエチレンの供給を再度開始した。１５分後、エチレンの流量を２Ｎｍ³／ｈに下げ、系内の圧力を０．８ｋｇ／ｃｍ²-Gにした。この間に、系内の温度は３５℃まで上昇した。その後、系内の温度を３２〜３５℃に調節しながら、エチレンを４Ｎｍ³／ｈの流量で３．５時間供給した。この間、系内の圧力は０．７〜０．８ｋｇ／ｃｍ²-Gに保持されていた。次いで、系内を窒素により置換を行った後、上澄み液を除去し、ヘキサンで２回洗浄した。このようにして固体触媒成分１ｇ当たり３ｇのポリマーが予備重合された予備重合触媒（ｂ）を得た。この予備重合したポリマーの極限粘度［η］は２．１ｄｌ／ｇであり、1-ヘキセンの含量は４．８重量％であった。
【００７８】
重合
充分に窒素置換した内容積１リットルのステンレス製オートクレーブにヘプタン５００ｍｌを装入し、系内をエチレンで置換した後、1-ヘキセン２０ｍｌ、上記で調製した予備重合触媒（ｂ）０．２８ｇを装入し、室温で１０分間保持した。その後、エパン７５０（第一工業製薬製、ポリアルキレンオキサイドブロック）７．５ｍｇ、上記で調製した予備重合触媒（ｂ）０．３８ｇを装入し、系内の温度を７０℃に昇温した。次いで、エチレンを導入することにより重合を開始した。その後、連続的にエチレンを供給しながら、８ｋｇ／ｃｍ²-G、８０℃の重合条件で１．５時間重合を行った。濾過によりポリマーを回収し、減圧下、８０℃で一晩乾燥することにより、メルトフローレートが０．１２ｇ／10分であり、密度が０．９２６ｇ／ｃｍ³であり、嵩比重が０．４２ｇ／ｃｍ³であるエチレン・1-ヘキセン共重合体２０８ｇを得た。また、重合器壁や攪拌羽根へのポリマーの付着は認められなかった。
【００７９】
（実施例２〜９）
重合
実施例１の重合において、エパン７５０（第一工業製薬製）の代わりに表１に示す化合物（Ｂ）を用いたこと以外は実施例１と同様にしてエチレンと1-ヘキセンとの共重合を行った。いずれの場合も、重合終了後の重合器壁や攪拌羽根へのポリマーの付着は認められなかった。結果を表1に示す。
【００８０】
（比較例１）
重合
実施例１の重合において、エパン７５０（第一工業製薬製）を用いなかったこと以外は実施例１と同様にしてエチレンと1-ヘキセンとの共重合を行った。重合終了後の重合器壁や攪拌羽根には多量のポリマーの付着が認められた。結果を表１に示す。
【００８１】
なお、表１中の表示は下記の通りである。
（B−１）ポリアルキレンオキサイドブロック、
（B−２）高級脂肪族アミド、
（B−３）アルキルジエタノールアミンおよび
（B−４）ポリオキシアルキレンアルキルアミン
（注１）第一工業製薬製 エパン７５０ 平均分子量４０００
エチレンオキサイド部分２０００ プロピレンオキサイド部分２０００
（注２）第一工業製薬製 エパン７２０ 平均分子量２５００
エチレンオキサイド部分５００ プロピレンオキサイド部分２０００
（注３）第一工業製薬製 エパン７１０ 平均分子量２２２０
エチレンオキサイド部分２２０ プロピレンオキサイド部分２０００
（注３）第一工業製薬製 エパン４２０ 平均分子量１５００
エチレンオキサイド部分３００ プロピレンオキサイド部分１２００
（注５）第一工業製薬製 エパン４１０ 平均分子量１３３０
エチレンオキサイド部分１３０ プロピレンオキサイド部分１２００
【００８２】
【表１】

[0001]
TECHNICAL FIELD OF THE INVENTION
  The present invention relates to an olefin slurry polymerization method, and more particularly to an olefin slurry polymerization method that provides an olefin polymer having high activity and excellent particle properties.
[0002]
TECHNICAL BACKGROUND OF THE INVENTION
  Olefin polymers such as polyethylene, polypropylene, ethylene / α-olefin copolymers, and propylene / α-olefin copolymers include, for example, a solid catalyst containing a metallocene compound of a Group 4 metal such as zirconium and an organoaluminum component. It is produced by (co) polymerizing olefins in the presence of a metallocene solid catalyst.
[0003]
  By the way, when slurry polymerization is performed in the presence of the metallocene-based solid catalyst as described above, a polymer lump, a sheet-like material, etc. are generated in the polymerization vessel, or the polymer adheres to the stirring blade and continuously stably for a long time. It may become impossible to drive, and improvements have been desired.
[0004]
  As a result of studying in view of such prior art, the present inventors have found that the use of a specific surfactant as a catalyst component reduces the above-described problems and does not lower the polymerization activity. The present invention has been completed.
[0005]
OBJECT OF THE INVENTION
  The present invention has been made in view of the prior art as described above, and an olefin polymer having high activity and excellent particle properties can be obtained, and there is little contamination on the wall of the polymerizer, which is stable over a long period of time. The present invention provides a method for obtaining an olefin polymer that can be operated continuously by a slurry polymerization method.
[0006]
SUMMARY OF THE INVENTION
  The olefin slurry polymerization method according to the present invention comprises:
(A)
(A-1) Group 4 transition metal compounds having a cyclopentadienyl skeleton,
(A-2) an organoaluminum oxy compound,
and
(A-3) Fine particle carrier
An olefin polymerization catalyst comprising:
(B)
(B-1) polyalkylene oxide block,
(B-2) a higher aliphatic amide,
(B-3) alkyldiethanolamine,
and
(B-4) At least one compound selected from polyoxyalkylene alkylamines
In the presence of olefin, an olefin is polymerized in a hydrocarbon medium to produce an olefin polymer.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
  Hereinafter, the olefin slurry polymerization method according to the present invention will be described in detail. In the present specification, the term “polymerization” may be used to mean not only homopolymerization but also copolymerization, and the term “polymer” refers not only to homopolymers but also to copolymerizations. It may be used in the meaning that also includes coalescence.
[0008]
  The olefin slurry polymerization method according to the present invention comprises:
(A)
(A-1) Group 4 transition metal compounds having a cyclopentadienyl skeleton,
(A-2) an organoaluminum oxy compound,
and
(A-3) Fine particle carrier
An olefin polymerization catalyst comprising:
(B)
(B-1) polyalkylene oxide block,
(B-2) a higher aliphatic amide,
(B-3) alkyldiethanolamine,
and
(B-4) At least one compound selected from polyoxyalkylene alkylamines
In the presence of the olefin, the olefin is polymerized in a hydrocarbon medium.
[0009]
  Hereinafter, the olefin polymerization catalyst used in the present invention will be described first.
(A) Olefin polymerization catalyst
(A) The olefin polymerization catalyst of the present invention comprises (A-1) a transition metal compound of Group 4 of the periodic table having a cyclopentadienyl skeleton, (A-2) an organoaluminum oxy compound, and (A-3) An olefin polymerization catalyst comprising a particulate carrier.
Below, each component which forms the catalyst support | carrier for olefin polymerization used by this invention is demonstrated.
[0010]
(A-1) Transition metal compounds
(A-1) 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 (I).
      ML_X (I)
In the formula, M is a transition metal of Group 4 of the periodic table, specifically, zirconium, titanium, or hafnium.
[0011]
  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, -SO_ThreeR (wherein R is a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent such as halogen) or a hydrogen atom.
[0012]
  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.
[0013]
  Among the ligands coordinated to these transition metals, an alkyl-substituted cyclopentadienyl group is particularly preferable. When the compound represented by the general formula (I) 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.
[0014]
  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.
[0015]
  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.
[0016]
  Examples of halogen include fluorine, chlorine, bromine and iodine. -SO_ThreeExamples of the ligand represented by R include a p-toluenesulfonate group, a methanesulfonate group, a trifluoromethanesulfonate group, and the like.
[0017]
  For example, when the valence of the transition metal is 4, the compound represented by the general formula (I) is more specifically represented by the following general formula (I ′).
        R¹R²R^ThreeR^FourM ... (I ')
Wherein M is zirconium, titanium or hafnium, and R¹ Is a group having a cyclopentadienyl skeleton and R² , R^Three And R^Four May be the same as or different from each other, a group having a cyclopentadienyl 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_ThreeR or a hydrogen atom. )
[0018]
  In the present invention, R in the general formula (I ′) is used.² , R^Three And R^Four Transition metal compounds in which one of them is a group having a cyclopentadienyl skeleton, such as R¹ And R²A transition metal compound in which is a group having a cyclopentadienyl 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^Three And R^Four Is 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_ThreeR or a hydrogen atom.
[0019]
  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,
Ethylene bis (indenyl) zirconium bis (methanesulfonate),
Ethylene bis (indenyl) zirconium bis (p-toluenesulfonate),
Ethylene bis (indenyl) zirconium bis (trifluoromethanesulfonate),
Ethylenebis (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,
Dimethylsilylene bis (dimethylcyclopentadienyl) zirconium dichloride,
Dimethylsilylene bis (trimethylcyclopentadienyl) zirconium dichloride,
Dimethylsilylenebis (indenyl) zirconium dichloride,
Dimethylsilylene bis (indenyl) zirconium bis (trifluoromethanesulfonate),
rac-dimethylsilylenebis {1- (2-methyl-4,5-acenaphthocyclopentadienyl)} zirconium dichloride,
rac-dimethylsilylenebis {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 dichloride,
Dimethylsilylene (cyclopentadienyl-fluorenyl) zirconium dichloride,
Diphenylsilylenebis (indenyl) zirconium dichloride,
Methylphenylsilylenebis (indenyl) zirconium dichloride,
Bis (cyclopentadienyl) zirconium dichloride,
Bis (cyclopentadienyl) zirconium dibromide,
Bis (cyclopentadienyl) methylzirconium monochloride,
Bis (cyclopentadienyl) ethylzirconium monochloride,
Bis (cyclopentadienyl) cyclohexyl zirconium monochloride,
Bis (cyclopentadienyl) phenylzirconium monochloride,
Bis (cyclopentadienyl) benzylzirconium monochloride,
Bis (cyclopentadienyl) zirconium monochloride 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 (dimethylcyclopentadienyl) 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 (trimethylsilylcyclopentadienyl) zirconium dichloride and the like.
[0020]
  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-.
[0021]
  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.
[0022]
(A-2) Organoaluminum oxy compounds
(A-2) Specifically, the organoaluminum oxy compound may be a conventionally known aluminoxane, or a benzene-insoluble organoaluminum oxy compound as disclosed in JP-A-2-276807. Also good.
[0023]
  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.
[0024]
(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.
[0025]
(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.
[0026]
  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.
[0027]
  Specific examples of organoaluminum compounds used in the preparation of 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 Dialkylaluminum such as diisobutylaluminum chloride Umuharaido 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.
[0028]
  Of these, trialkylaluminum and tricycloalkylaluminum are particularly preferred. In addition, as this organoaluminum compound, the following general formula
(I-C_FourH₉)_xAl_y(C_FiveH_Ten)_z
Isoprenyl aluminum represented by (x, y, z is a positive number and z ≧ 2x) can also be used.
[0029]
  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.
[0030]
(A-3) Particulate carrier
(A-3) Specifically, as a particulate carrier, SiO₂ , Al₂O_Three , MgO, ZrO₂ TiO₂ , B₂O_Three , CaO, ZnO, BaO, ThO₂ Or a mixture containing these, for example SiO₂-MgO, SiO₂-Al₂O_Three , SiO₂-TiO₂ , SiO₂-V₂O_Five , SiO₂-Cr₂O_Three , SiO₂-TiO₂Examples thereof include inorganic carriers such as -MgO, and organic carriers such as polyethylene, polypropylene, poly 1-butene, poly 4-methyl-1-pentene, and styrene-divinylbenzene copolymer.
[0031]
  Such (A-3) fine particle carrier desirably 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 the (A-1) group 4 transition metal compound having a cyclopentadienyl skeleton, the (A-2) organoaluminum oxy compound, The (A-3) fine particle carrier is contained as an essential component, but (C) an organoaluminum compound may be contained as required.
[0032]
  As such (C) organoaluminum compound, for example, an organoaluminum compound represented by the following general formula (II) can be exemplified.
R^a _nAlX_3-n … (II)
(Wherein R^aRepresents a hydrocarbon group having 1 to 12 carbon atoms, X represents a halogen atom or a hydrogen atom, and n is 1 to 3. )
[0033]
  In the general formula (II), R^aIs a hydrocarbon group having 1 to 12 carbon atoms, such as an alkyl group, a cycloalkyl group or an aryl group, and specifically includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an isobutyl group, a pentyl group. Group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group, tolyl group and the like.
[0034]
  Specific examples of the organoaluminum compound (C) 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; Aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, alkyl aluminum dihalides such as ethyl aluminum dibromide; diethylaluminum hydride, and alkyl aluminum hydride such as diisobutyl aluminum hydride.
[0035]
  Further, as the organoaluminum compound (C), a compound represented by the following general formula (III) can also be used.
R^a _nAlY_3-n (III)
(Wherein R^aIs the same as above, and Y is -OR.^bGroup, -OSiR^c _ThreeGroup, -OAlR^d ₂Group, -NR^e ₂Group, -SiR^f _ThreeGroup or -N (R^g) AlR^h ₂A group, n is 1-2, R^b, R^c, R^dAnd R^hIs a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group or the like;^eIs a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, a phenyl group, a trimethylsilyl group, etc., and R^fAnd R^gIs a methyl group, an ethyl group or the like. )
[0036]
  Specific examples of such an organoaluminum compound include the following compounds.
(1) R^a _nAl (OR^b)_3-nFor example, dimethylaluminum methoxide, diethylaluminum ethoxide, diisobutylaluminum methoxide,
(2) R^a _nAl (OSiR^c _Three)_3-nA compound represented by, for example, Et₂Al (OSiMe_Three), (Iso-Bu)₂Al (OSiMe_Three), (Iso-Bu)₂Al (OSiEt_Three)Such;
(3) R^a _nAl (OAlR^d ₂)_3-nA compound represented by, for example, Et₂AlOAlEt₂, (Iso-Bu)₂AlOAl (iso-Bu)₂Such;
(4) R^a _nAl (NR^e ₂)_3-nA compound represented by, for example, Me₂AlNEt₂, Et₂AlNHMe, Me₂AlNHEt, Et₂AlN (SiMe_Three)₂, (Iso-Bu)₂AlN (SiMe_Three)₂Such;
(5) R^a _nAl (SiR^f _Three)_3-nA compound represented by, for example, (iso-Bu)₂AlSiMe_ThreeSuch;
(6) R^a _nAl (N (R^g) AlR^h ₂)_3-nA compound represented by, for example, Et₂AlN (Me) AlEt₂, (Iso-Bu)₂AlN (Et) Al (iso-Bu)₂Such.
  Among the organoaluminum compounds represented by the general formula (II) or (III), the general formula R^a _ThreeAl, R^a _nAl (OR^b)_3-n, R^a _nAl (OAlR^d ₂)_3-nAre preferred, particularly R^aIs an isoalkyl group and n = 2 is preferred.
[0037]
Support-supported metallocene catalyst
  The carrier-supported metallocene catalyst preferably used in the present invention includes (A-1) the transition metal compound of Group 4 of the periodic table having a cyclopentadienyl skeleton, and (A-2) the organoaluminum oxy compound. The (A-3) particulate carrier and, if necessary, the (C) organoaluminum compound.
[0038]
  Such a carrier-supported metallocene catalyst includes (A-1) a transition metal compound of Group 4 of the periodic table having a cyclopentadienyl skeleton, (A-2) an organoaluminum oxy compound, (A-3) It can be prepared by mixing and contacting the fine particle carrier and (C) an organoaluminum compound as required. The contact order of each component is arbitrarily selected.
[0039]
  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, or mixtures thereof.
[0040]
  In preparing the carrier-supported metallocene catalyst, the (A-1) transition metal compound is usually 0.001 to 1.0 mmol, preferably 0, in terms of transition metal atoms, per 1 g of (A-3) particulate carrier. 0.005 to 0.5 mmol is used, and the (A-2) organoaluminum oxy compound is generally used in an amount of 0.1 to 100 mmol, preferably 0.5 to 20 mmol, in terms of aluminum atoms. When (C) 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 (A-3) particulate carrier.
[0041]
  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.
[0042]
  The carrier-supported metallocene catalyst thus obtained has about 5 × 10 (A-1) transition metal compound in terms of transition metal atom per gram of (A-3) particulate carrier.^-6-10^-3Moles, preferably 10^-Five~ 3x10^-FourIt is supported in a molar amount, and (A-2) an organoaluminum oxy compound (including (C) an organoaluminum compound, if necessary, including its aluminum) is about 10 in terms of aluminum atom.^-3-10^-1Moles, preferably 2 × 10^-3~ 5x10^-2It is preferably supported in molar amounts.
[0043]
  The olefin polymerization catalyst used in the present invention may be prepolymerized with olefin. The prepolymerization catalyst is formed from the (A) olefin polymerization catalyst, the (C) organoaluminum compound as required, and (D) an olefin polymer produced by prepolymerization.
[0044]
  The prepolymerization catalyst as described above includes the (A-1) transition metal compound, the (A-2) organoaluminum oxy compound, the (A-3) particulate carrier, and the (C) as necessary. It is preferably formed from an organoaluminum compound and (D) an olefin polymer produced by preliminary polymerization.
[0045]
  As a method for preparing such a prepolymerization catalyst, for example, an (A-1) transition metal compound, (A-2) an organoaluminum oxy compound, and (A-3) a particulate carrier are inert hydrocarbon solvents. There is a method in which a small amount of olefin is preliminarily polymerized to a solid catalyst component obtained by mixing and contacting in or in an olefin medium.
[0046]
  In addition, (C) organoaluminum compound can be used at the time of prepolymerization. Examples of the inert hydrocarbon solvent used in the preparation of the prepolymerization catalyst include the same inert hydrocarbon solvents used in preparing the carrier-supported metallocene catalyst.
[0047]
  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%.
[0048]
  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, 1-eicosene.
[0049]
  Further, 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.
[0050]
  In preparing the prepolymerization catalyst, the (A-1) transition metal compound is usually 0.001 to 1.0 mmol, preferably 0.005 to 1 g of (A-3) fine particle support, in terms of transition metal atoms. It is used in an amount of 0.5 mmol, and the (A-2) 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 atoms. When (C) an organoaluminum compound is used, it is generally used in an amount of 0.001 to 1000 mmol, preferably 0.01 to 500 mmol, per 1 g of (A-3) particulate carrier.
[0051]
  The prepolymerization catalyst obtained as described above has about 5 × 10 (A-1) transition metal compound in terms of transition metal atom per 1 g of (A-3) particulate carrier.^-6-10^-3Moles, preferably 10^-Five~ 3x10^-FourIt is supported in a molar amount, and (A-2) organoaluminum oxy compound is about 10 in terms of aluminum atom.^-3-10^-1Moles, preferably 2 × 10^-3~ 5x10^-2The olefin polymer (D) supported in a molar amount and produced by prepolymerization is supported in an amount of about 0.1 to 500 g, preferably 0.3 to 300 g, particularly preferably 1 to 100 g. desirable.
[0052]
  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.
[0053]
  Next, the compound (B) used in the present invention will be described.
(B-1) Polyalkylene oxide block
  The (B-1) polyalkylene oxide block used in the present invention is generally used as a nonionic surfactant, and any conventionally known polyalkylene oxide block can be used without any limitation.
The polyalkylene oxide block has a general formula
HO- (CH₂CH₂O)_m-{CH₂CH (CH_Three) O}_n-(CH₂CH₂O)_pA polyethylene oxide-polypropylene oxide-polyethylene oxide block represented by H is preferred.
[0054]
  In the above general formula (CH₂CH₂M representing the average chain length of the oxyethylene unit represented by O) is desirably in the range of 1-30, preferably 1-20, more preferably 1-10, and p is 1-30, preferably Is preferably in the range of 1-20, more preferably 1-10, and {CH₂CH (CH_ThreeN) indicating the average chain length of the oxypropylene unit represented by O} is desirably in the range of 2 to 50, preferably 3 to 45, more preferably 4 to 40.
[0055]
  Further, as a suitable polyalkylene oxide block, the general formula
HO- {CH₂CH (CH_Three) O}_a-(CH₂CH₂O)_b-{CH₂CH (CH_Three) O}_cExamples thereof include a polypropylene oxide-polyethylene oxide-polypropylene oxide block represented by H 2.
[0056]
  In the above general formula (CH₂CH₂B representing the average chain length of the oxyethylene unit represented by O) is desirably in the range of 1 to 50, preferably 1 to 40, more preferably 2 to 30, and {CH₂CH (CH_ThreeA) indicating the average chain length of the oxypropylene unit represented by O} is in the range of 2 to 30, preferably 3 to 25, more preferably 4 to 20, and c is 2 to 30, The range is preferably 3 to 25, more preferably 4 to 20.
[0057]
(B-2) Higher aliphatic amides
  The (B-2) higher aliphatic amide used in the present invention is generally used as a nonionic surfactant, and any conventionally known higher aliphatic amide can be used without any limitation.
Higher aliphatic amides have the general formula
(C_mH_{2m + 1}CO) N (CH₂CH₂OH)₂
An alkyldiethanolamide represented by the formula is preferably used.
In the above general formula (C_mH_{2m + 1}M indicating the number of carbon atoms of the alkyl group represented by) is 1 to 30, preferably 6 to 20, and more preferably 8 to 18.
[0058]
  Specific examples of the higher aliphatic amide include lauryl diethanolamide, cetyl diethanolamide, stearyl diethanolamide, octyl diethanolamide, nonyl diethanolamide, sec-lauryl diethanolamide, and the like. Of these, lauryl diethanolamide is preferred.
[0059]
(B-3) Alkyldiethanolamine
  The (B-3) alkyldiethanolamine used in the present invention is generally used as a nonionic surfactant, and any conventionally known alkyldiethanolamine can be used without any limitation.
[0060]
  As alkyldiethanolamine, general formula
(C_mH_{2m + 1}) N (CH₂CH₂OH)₂
The thing represented by is mentioned. In the above general formula (C_mH_{2m + 1}M representing the number of carbon atoms of the alkyl group represented by () is desirably in the range of 1 to 30, preferably 6 to 20, and more preferably 8 to 18. Specific examples of the alkyldiethanolamine include lauryl diethanolamine, cetyl diethanolamine, stearyl diethanolamine, octyl diethanolamine, nonyl diethanolamine, sec-lauryl diethanolamine, and the like. Of these, lauryl diethanolamine is preferred.
[0061]
(B-4) Polyoxyalkylene alkylamine
  The (B-4) polyoxyalkylene alkylamine used in the present invention is generally used as a nonionic surfactant, and any conventionally known polyoxyalkylene alkylamine can be used without any limitation.
[0062]
  The polyoxyalkylene alkylamine has a general formula
(C_mH_{2m + 1}) N {(CH₂CH₂O)_nH} {(CH₂CH₂O)_pH}
The polyoxyethylene alkylamine represented by these is mentioned. In the above general formula (C_mH_{2m + 1}M representing the number of carbon atoms of the alkyl group represented by) is desirably in the range of 1 to 30, preferably 6 to 20, more preferably 8 to 18, and (CH₂CH₂N and p which show the average chain length of the oxyethylene unit represented by O) may be the same or different and are in the range of 2-40, preferably 2-30, more preferably 2-20. It is desirable.
[0063]
  Of the compounds (B) as described above, (B-1) polyalkylene oxide block, (B-3) alkyldiethanolamine, (B-4) polyoxyalkylene alkylamine are preferably used, An alkylene oxide block, (B-4) polyoxyalkylene alkylamine is more preferably used, and (B-1) polyalkylene oxide block is particularly preferably used.
[0064]
  In the present invention, an olefin is polymerized by a slurry polymerization method in the presence of the above (A) olefin polymerization catalyst and the compound (B).
[0065]
  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%.
[0066]
  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.
[0067]
  Examples of the inert hydrocarbon medium used for slurry polymerization include the same inert hydrocarbon solvents used in preparing the carrier-supported metallocene catalyst. Of these inert hydrocarbon solvents, aliphatic hydrocarbons and alicyclic hydrocarbons are preferred.
[0068]
  In the polymerization, the olefin polymerization catalyst is usually 10 per liter of polymerization volume in terms of transition metal atoms in the Group 4 transition metal compound (A-1).^-8-10^-3Moles, preferably 10^-7-10^-FourIt is desirable to be used in molar amounts. The organoaluminum oxy compound (A-2) is used in an amount of 10 to 500 mol, preferably 20 to 200 mol per mol of transition metal atom in the Group 4 transition metal compound (A-1) in terms of aluminum atom. It is desirable that
[0069]
  The compound (B) is desirably used in an amount of usually 0.1 to 500 mg, preferably 0.2 to 200 mg, particularly preferably 0.5 to 100 mg per liter of polymerization volume. In the polymerization, if necessary, (A-3) an organoaluminum oxy compound and / or (C) an organoaluminum compound not supported on a particulate carrier can be used. In terms of conversion, usually 10 per liter of polymerization volume^-3Mol or less, preferably 5 × 10^-FourMol or less, more preferably 2 × 10^-FourIt is desirable to be used in an amount of less than a mole.
[0070]
  The polymerization temperature of the olefin is usually −50 to 100 ° C., preferably 0 to 90 ° C. The polymerization pressure is usually from normal pressure to 100 kg / cm.², Preferably normal pressure to 50 kg / cm²The polymerization reaction can be carried out in any of batch, semi-continuous and continuous methods. Furthermore, the polymerization can be carried out in two or more stages having different reaction conditions. The molecular weight of the resulting olefin polymer can be adjusted by allowing hydrogen to be present in the polymerization system or changing the polymerization temperature.
[0071]
【The invention's effect】
  In the olefin slurry polymerization method according to the present invention, an olefin polymer having excellent particle properties can be obtained with high polymerization activity, and the contamination of the polymerizer wall is small.
[0072]
【Example】
  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.
[0073]
  In this example, the autoclave wall condition score was as follows.
[0074]
    ○ ... No polymer was found on the wall of the autoclave
    ×… Adherence of polymer to the wall of the autoclave was observed
In addition, the outline of the slurry polymerization method in a present Example is as follows.

That is, heptane was charged into a polymerization vessel, and the system was replaced with ethylene. Then, hexene-1 and a polymerization catalyst (referred to as (1) -1) were charged and held for about 10 minutes. Thereafter, the polymerization catalyst (referred to as (1) -2) was charged again, and the compound (B) was added. The inside of the system was pressurized with ethylene and heated to carry out polymerization. In normal polymerization, alkylaluminum such as triisobutylaluminum is used as a scavenger at the catalyst (1) -1 in the above figure. However, since alkylaluminum itself also acts as an antistatic agent, compound (B) (antistatic The agent cannot be evaluated. Therefore, in this example, catalyst (1) is used as a scavenger instead of alkylaluminum. If catalyst (1) -1 is not used in the above figure, the polymer yield will be extremely low. Since some active sites of the catalyst (1) -2 are deactivated by impurities in the system, a polymer is hardly obtained unless the catalyst (1) -2 is used in the above diagram. This is because almost all of the aluminum (derived from aluminoxane) contained in the catalyst (1) -1 functions as a scavenger, and most of the active sites of the catalyst (1) -1 are deactivated.
[0075]
Example 1
Preparation of solid catalyst component (a)
  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.
[0076]
  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 (a) containing 3.2 mg of zirconium per 1 g of the solid catalyst component.
[0077]
Preparation of prepolymerization catalyst (b)
  A 350 liter reactor sufficiently purged with nitrogen was charged with 7.0 kg of the solid catalyst component prepared above and hexane to make the total volume 285 liters. After cooling the system to 10 ° C, ethylene is 8 Nm.^ThreeBlowing into hexane for 5 minutes at a flow rate of / h. 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. 8Nm after the system is closed^ThreeThe ethylene supply was started again at a flow rate of / h. After 15 minutes, the ethylene flow rate is 2 Nm^Three/ H, and the pressure in the system is 0.8 kg / cm²-G. During this time, the temperature in the system rose to 35 ° C. Thereafter, ethylene was adjusted to 4 Nm while adjusting the temperature in the system to 32 to 35 ° C.^Three/ H was supplied for 3.5 hours. During this time, the pressure in the system is 0.7 to 0.8 kg / cm.²-G was held. Next, after the inside of the system was replaced with nitrogen, the supernatant was removed and washed twice with hexane. Thus, a prepolymerized catalyst (b) 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.
[0078]
polymerization
  500 ml of heptane was charged into a 1 liter stainless steel autoclave thoroughly purged with nitrogen, and the system was replaced with ethylene. Then, 20 ml of 1-hexene and 0.28 g of the prepolymerized catalyst (b) prepared above were loaded. And kept at room temperature for 10 minutes. Thereafter, 7.5 mg of Epan 750 (Daiichi Kogyo Seiyaku, polyalkylene oxide block) and 0.38 g of the prepolymerized catalyst (b) prepared above were charged, and the temperature in the system was raised to 70 ° C. Then, polymerization was started by introducing ethylene. Then, while continuously supplying ethylene, 8 kg / cm²Polymerization was carried out for 1.5 hours under polymerization conditions of -G and 80 ° C. The polymer is recovered by filtration and dried overnight at 80 ° C. under reduced pressure to give a melt flow rate of 0.12 g / 10 min and a density of 0.926 g / cm.^ThreeThe bulk specific gravity is 0.42 g / cm^ThreeAs a result, 208 g of an ethylene / 1-hexene copolymer was obtained. Moreover, adhesion of the polymer to the polymerization vessel wall and the stirring blade was not recognized.
[0079]
(Examples 2-9)
polymerization
  In the polymerization of Example 1, ethylene and 1-hexene were copolymerized in the same manner as in Example 1 except that the compound (B) shown in Table 1 was used instead of Epan 750 (Daiichi Kogyo Seiyaku). went. In any case, the adhesion of the polymer to the polymerization vessel wall and the stirring blade after the polymerization was not observed. The results are shown in Table 1.
[0080]
(Comparative Example 1)
polymerization
  In the polymerization of Example 1, ethylene and 1-hexene were copolymerized in the same manner as in Example 1 except that Epan 750 (Daiichi Kogyo Seiyaku Co., Ltd.) was not used. Adhesion of a large amount of polymer was observed on the wall of the polymerization vessel and the stirring blade after completion of the polymerization. The results are shown in Table 1.
[0081]
  In addition, the display in Table 1 is as follows.
(B-1) a polyalkylene oxide block,
(B-2) a higher aliphatic amide,
(B-3) alkyldiethanolamine and
(B-4) Polyoxyalkylene alkylamine
(Note 1) Epan 750 average molecular weight 4000 made by Daiichi Kogyo Seiyaku
Ethylene oxide part 2000 Propylene oxide part 2000
(Note 2) Epan 720 average molecular weight 2500 from Daiichi Kogyo Seiyaku
Ethylene oxide part 500 Propylene oxide part 2000
(Note 3) Epan 710 average molecular weight 2220 manufactured by Daiichi Kogyo Seiyaku
Ethylene oxide portion 220 Propylene oxide portion 2000
(Note 3) Epan 420 average molecular weight 1500 from Daiichi Kogyo Seiyaku
Ethylene oxide portion 300 Propylene oxide portion 1200
(Note 5) Epan 410 average molecular weight 1330, manufactured by Daiichi Kogyo Seiyaku
Ethylene oxide portion 130 Propylene oxide portion 1200
[0082]
[Table 1]

Claims (1)

(A)
(A-1) Group 4 transition metal compounds having a cyclopentadienyl skeleton,
(A-2) an organoaluminum oxy compound,
and
(A-3) an olefin polymerization catalyst comprising a particulate carrier;
(B)
(B-1) polyalkylene oxide block,
(B-2) a higher aliphatic amide,
(B-3) alkyldiethanolamine,
and
(B-4) An olefin slurry characterized in that an olefin polymer is produced by polymerizing an olefin in a hydrocarbon medium in the presence of at least one compound selected from polyoxyalkylene alkylamines. Polymerization method.