JP2004018785A - Method for producing propylene polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a propylene polymer giving polymer particles having a high bulk density with a high polymerization activity without accompanying fouling in the production of a propylene copolymer, and a polymer suppressed with the reduction of melting point in the production of a propylene homopolymer. <P>SOLUTION: This method for producing the propylene polymer comprises performing the polymerization or copolymerization of propylene by using a polymerization catalyst consisting of (A) a solid co-catalyst obtained by chemically bonding a non-coordinated ion-containing compound on a fine particle carrier, (B) a metallocene compound and (C) an organometallic compound and feeding (D) a nonionic surfactant into a polymerization vessel so as to become 0.1-100.0 mg range based on 1 kg polymerization reaction mixture in the polymerization system. <P>COPYRIGHT: (C)2004,JPO

Description

【０１２９】
実施例１１
１）重合用触媒の調製
乾燥して窒素置換した３０ｍｌフラスコに成分（Ａ−１）を３０ｍｇ採取後、（Ｂ）としてＭＮＩＺおよび（Ｃ）としてＴＮＯＡを含むヘキサン溶液（それぞれ０．５ミリモル／Ｌおよび０．５モル／Ｌ）を１．８ｍｌ加え、３０℃で３０分間撹拌した。室温まで冷却後、０．０７モル／ＬのＴＩＢＡ−ヘキサン溶液５．４ｍｌを加えて重合用触媒を得た。
【０１３０】
２）プロピレンの予備重合
乾燥し、窒素置換した三方コック付の１００ｍｌナス型フラスコをプロピレンガスで置換した。次いで、三方コックに窒素を流しながら、三方コックから上記で調製した重合用触媒の全量を添加し、室温で２時間攪拌して、予備重合を行った。
【０１３１】
３）プロピレンとエチレンの共重合
１．５リットルのオートクレーブに０．５モル／ＬのＴＩＢＡ−ヘキサン溶液を１ｍｌ、成分（Ｄ）として（Ｄ−１−１）を１．０ｍｇおよびプロピレンを８モル加え、６５℃に昇温した後、上記２）で予備重合した重合用触媒（固体助触媒成分（Ａ）として９ｍｇ）をオートクレーブ中に圧入し、重合を開始した。重合開始１分後、エチレンをその分圧が０．２５ＭＰａとなるまで導入し、７０℃でプロピレンとエチレンを共重合させた。エチレンの導入から１５分後、メタノールを圧入することで重合を停止させた。未反応のプロピレンを除去し、プロピレン共重合体を得た。結果を表２に示す。
【０１３２】
実施例１２〜２３
表２に記載の各成分を用いたことを除き実施例１１と同じ操作を繰り返して、プロピレン共重合体を得た。結果を表２に示す。
【０１３３】
実施例２４
ＭＮＩＺの使用量を２倍にしたことを除き実施例１１と同じ操作を繰り返して、プロピレン共重合体を得た。結果を表２に示す。
【０１３４】
比較例９
成分（Ｄ）の使用量を表２に記載の値としたことを除き実施例１１と同じ操作を繰り返して、プロピレン共重合体を得た。結果を表２に示す。
【０１３５】
比較例１０
成分（Ｄ）を使用しなかったことを除き実施例１６と同じ操作を繰り返して、プロピレン共重合体を得。結果を表２に示す。
【０１３６】
比較例１１
成分（Ｄ）の使用量を表２に記載の値としたことを除き実施例２１と同じ操作を繰り返した。結果を表２に示す。
【０１３７】
比較例１２
成分（Ｄ）としてイオン性界面活性剤であるセチルトリメチルアンモニウムクロライド（Ｄ−７）を使用したことを除き実施例１１と同じ操作を繰り返して、プロピレン共重合体を得た。結果を表２に示す。
【０１３８】
比較例１３および１４
成分（Ａ）として、比較例３で調製した（Ａ−４）またはシリカ担持メチルアルミノキサン（Ａ−５）をそれぞれ用いたことを除き実施例１１と同じ操作を繰り返した。結果を表２に示す。
【０１３９】
比較例１５
実施例１において成分（Ｄ）をオートクレーブに添加せずに重合用触媒の調製時に添加したことを除き実施例１１と同じ操作を繰り返した。結果を表２に示す。
【０１４０】
【表２】

【０１４１】
【発明の効果】
以上に説明したように、本発明によれば、プロピレン共重合体を製造した場合にもファウリングを伴うことがなく、嵩密度の高い重合体粒子を、高い重合活性で得ることができ、かつ、プロピレン単独重合体の製造時には融点の低下が抑制されたプロピレン重合体を得ることができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for producing a propylene polymer. In particular, the present invention relates to a method for producing a propylene polymer capable of providing a polymer having a high bulk density without fouling.
[0002]
[Prior art]
In recent years, many proposals have been made to produce a high bulk density olefin polymer by supporting a metallocene catalyst on a fine particle carrier. For example, WO 96/41808 discloses a catalyst comprising a solid co-catalyst component in which a non-coordinating ion-containing compound is chemically bonded to a fine particle carrier, a metallocene compound and an organoaluminum compound. It is described that performing polymerization gives a polymer having a relatively high bulk density without fouling. However, when propylene is polymerized at a temperature of about 70 ° C., which is industrially significant, the suppression of fouling and the bulk density of the polymer are still insufficient, and particularly, these have a large comonomer content. There is a problem that it is significant when a copolymer or a polymer having a low molecular weight is produced.
[0003]
Japanese Patent Application Laid-Open No. 2000-327707 discloses a method in which a non-ionic surfactant is added to a polymerization reactor to suppress the formation of a sheet or a lump. It describes that a polymer containing ethylene as a main component is produced by a catalyst comprising a methylaluminoxane and a metallocene compound. However, in this method, although it is possible to suppress the formation of a sheet or a lump, the bulk density of the obtained polymer particles is not necessarily improved. That is, in the examples of the above-mentioned publications, it is recognized that the bulk density is rather lowered in many cases, and that the polymerization activity is significantly lowered in not less than a few cases.
[0004]
Further, when the method specifically described in the above publication is applied to the production of a propylene polymer, the effect is insufficient compared to the case of the production of an ethylene polymer, and further improvement is desired.
[0005]
Further, for example, Japanese Patent Application Laid-Open No. 10-60032 discloses a catalyst comprising a metallocene compound and an antistatic agent, and a catalyst comprising aluminoxane and metallocene supported in the presence of a cationic antistatic agent at 60 ° C. The results of the polymerization of propylene are described. Although this method can suppress the formation of coarse particles, it is still insufficient in terms of the bulk density of the obtained polymer particles, and its effect is insufficient particularly in the production of a propylene copolymer. is there. Furthermore, there is a problem that the melting point of the obtained polymer is lower than when no antistatic agent is used.
[0006]
Further, the polymerization activity is extremely low, and when the polymerization temperature is increased to improve the polymerization activity, not only the bulk density is further reduced, but also fouling occurs. Further, in the examples of the above publication, when a solid promoter component in which the non-coordinating ion-containing compound described in WO96 / 41808 is chemically bonded to a fine particle carrier is used as the promoter component, the bulk density is still insufficient. Instead, fouling may occur.
[0007]
Japanese Patent Publication No. Hei 10-511706 discloses a catalyst comprising a metallocene catalyst component, a porous carrier, an aluminoxane and a surface modifier. Specifically, a catalyst component comprising a metallocene catalyst component, a porous carrier and an aluminoxane is disclosed. And then adding a surface modifier to the catalyst component. However, when propylene is polymerized by adding a surface modifier to a polymerization reactor as seen in Comparative Examples, not only the effect of the addition is not recognized, but also a significant decrease in polymerization activity is caused. It is described.
[0008]
Further, when the modifier is added to the polymerization reactor, the bulk density of the obtained propylene polymer decreases, which is also a problem in the production of the copolymer. Further, in the above publication, a solid cocatalyst component in which a non-coordinating ion-containing compound described in WO96 / 41808 is chemically bonded to a fine particle carrier is used instead of the catalyst component comprising a metallocene catalyst component, a porous carrier, and an aluminoxane. In such a case, the catalytic activity is significantly reduced.
[0009]
[Problems to be solved by the invention]
The present invention has been made in view of the problems of the prior art as described above, and even when a propylene copolymer is produced, without accompanying fouling, a polymer particle having a high bulk density can be provided with high polymerization activity. Also, it is an object of the present invention to provide a method for producing a propylene polymer which can provide a polymer in which the decrease in melting point is suppressed when producing a propylene homopolymer.
[0010]
[Means for Solving the Problems]
The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, as a co-catalyst component and a surfactant, a solid co-catalyst component and a non-ionic The present inventors have found that the above problems can be solved by polymerizing or copolymerizing propylene in the presence of a nonionic surfactant in a specific concentration range using a nonionic surfactant, and have accomplished the present invention.
[0011]
That is, in order to solve the above-mentioned problems, the present invention comprises (A) a solid promoter component in which a non-coordinating ion-containing compound is chemically bonded on a fine particle carrier, (B) a metallocene compound, and (C) an organometallic compound. The polymerization catalyst is used to supply (D) the nonionic surfactant to the polymerization reactor so as to be in a range of 0.1 to 100.0 mg per 1 kg of the polymerization reaction mixture in the polymerization system, thereby polymerizing propylene or Provided is a method for producing a propylene polymer, which comprises copolymerizing.
[0012]
BEST MODE FOR CARRYING OUT THE INVENTION
In the present invention, the solid co-catalyst component (A) in which the non-coordinating ion-containing compound is chemically bonded on the fine particle carrier is a non-coordinating ion-containing compound used as a co-catalyst in the metallocene catalyst. Are linked by Examples of the chemical bond include a covalent bond, an ionic bond, and a coordinate bond. By using a solid co-catalyst component in which a non-coordinating ion-containing compound is bonded to a fine particle carrier by a chemical bond, fouling and mutual adhesion of polymer particles are significantly suppressed, and a great effect is particularly obtained in bulk polymerization. Can be seen.
[0013]
These are described in, for example, JP-A-7-501573, JP-A-8-143617, WO96 / 40796, WO96 / 41808, WO97 / 19959, JP2000-212225, and the like. 1) A method for preparing a carrier by contacting a compound serving as a carrier with a non-coordinating ion-containing compound reactive with the carrier; 2) A non-coordinating ion having a functional group capable of forming a carrier 3) a method of preparing a carrier by forming a carrier from the containing compound and, if necessary, a precursor of the carrier; and 3) reacting the precursor of the non-coordinating ion-containing compound with the carrier to form a non-coordinating compound on the carrier. It is produced by a method for producing an ion-containing compound.
[0014]
A specific example of the method 1) is a method in which a non-coordinating ion-containing compound having a silyl halide group, an acid anhydride group or an acid chloride group is brought into contact with a carrier having a hydroxyl group such as silica or alumina. it can. A method of contacting a non-coordinating ion-containing compound having a hydroxyl group or a phenoxy group with a carrier such as silica or alumina treated with chlorosilane or organoaluminum is also exemplified. Further, a method of contacting a non-coordinating ion-containing compound having an electron donating group such as an alkoxy group, an alkoxysilyl group or an amino group with an electron accepting carrier such as magnesium chloride or alumina is also exemplified.
[0015]
As a specific example of the method 2), a method of forming a carrier by homopolymerizing or copolymerizing a non-coordinating ion-containing compound having a polymerizable group such as a vinyl group is exemplified. In addition, a method of forming a carrier by condensing a non-coordinating ion-containing compound having a condensable group such as an alkoxysilyl group alone or with another alkoxysilane or the like is also exemplified.
[0016]
As a specific example of the method 3), there is a method in which a non-coordinating ion-containing compound precursor such as triarylborane is reacted with a metalized support such as polystyrene to form a non-coordinating ion-containing compound. Is exemplified.
[0017]
Incidentally, the presence or absence of the chemical bond, for example, after washing at room temperature with a non-coordinating ion-containing compound such as dichloromethane or a polar solvent inert to the carrier, the non-coordinating ion-containing compound or this compound It can be detected by measuring whether the contained boron atom or the like remains on the fine particle carrier.
[0018]
Among them, (A) is preferably obtained by contacting a non-coordinating ion-containing compound (a-1) represented by the following formula (1) with a particulate carrier (a-2). .
[0019]
[M ¹ (R ¹ ) _a (R ² ) _b (R ³ ) _c (R ⁴ -L) _d ] ⁻ ・ [M ² X _e ] ⁺ (1)
Where M ¹ Is a boron or aluminum atom, preferably a boron atom.
[0020]
R ¹ , R ² And R ³ May be the same or different and are each independently a hydrocarbon having 1 to 20 carbon atoms or a halogenated hydrocarbon group, an alkoxy group, an aryloxy group or a halogen atom. Examples of the hydrocarbon group include an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, a phenyl group, a tolyl group, and a dimethylphenyl group. And the like. Examples of the halogenated hydrocarbon group include a halogenated aryl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, and a propoxy group. Examples of the aryloxy group include a phenoxy group, a naphthoxy group, a fluorophenoxy group, a pentafluorophenoxy group, and the like. Among these, preferred are an alkyl group, an aryl group and a halogenated aryl group, and particularly preferred are an aryl group and a halogenated aryl group.
[0021]
Specific examples of the halogenated aryl group include a fluorophenyl group such as a 4-fluorophenyl group, a difluorophenyl group such as a 2,4-difluorophenyl group and a 3,5-difluorophenyl group, and a 2,4,5-trifluoro group. Phenyl group, trifluorophenyl group such as 2,4,6-trifluorophenyl group, tetrafluorophenyl group such as 2,3,5,6-tetrafluorophenyl group, pentafluorophenyl group, 3,4-bis ( Bis (trifluoromethyl) phenyl group such as trifluoromethyl) phenyl group and 3,5-bis (trifluoromethyl) phenyl group, 2,3,5-tris (trifluoromethyl) phenyl group, 2,4,6 A tris (trifluoromethyl) phenyl group such as a tris (trifluoromethyl) phenyl group, 2,3,5,6-tetrakis Examples include tetrakis (trifluoromethyl) phenyl group such as trifluoromethyl) phenyl group, pentakis (trifluoromethyl) phenyl group and the like, and those in which fluorine atoms are replaced with other halogen atoms such as chlorine atom and bromine atom. Can be
[0022]
Among these halogenated aryl groups, fluorophenyl groups such as trifluorophenyl group, tetrafluorophenyl group, and pentafluorophenyl group, and bis (trifluoromethyl) phenyl groups such as 3,5-bis (trifluoromethyl) phenyl group Groups are preferable, and a tetrafluorophenyl group and a pentafluorophenyl group are more preferable, and a pentafluorophenyl group is particularly preferable.
[0023]
In the ionic compound (a-1), R ⁴ Is a hydrocarbon group having 1 to 20 carbon atoms and optionally containing a hetero atom, specifically, an alkylene group such as a methylene group, an ethylene group, a propylene group, a butylene group, an ethylidene group, a propylidene group; Bis (trifluoromethyl) phenylene such as phenylene, m-phenylene, p-phenylene, 3,5-bis (trifluoromethyl) -p-phenylene, 4-fluoro-m-phenylene, 2- A fluorophenylene group such as a fluoro-p-phenylene group; a difluorophenylene group such as a 4,5-difluoro-m-phenylene group; a 3,5-difluoro-p-phenylene group; and 2,4,5-trifluoro-m- Phenylene group, 2,4,6-trifluoro-m-phenylene group, 4,5,6-trifluoro-m-phenylene group, 2,3,5-trifluoro Trifluorophenylene groups such as low-p-phenylene group, 2,3,6-trifluoro-p-phenylene group, 3,4,5,6-tetrafluoro-o-phenylene group, 2,4,5,6 Arylene groups such as tetrafluoro-m-phenylene group, tetrafluorophenylene group such as 2,3,5,6-tetrafluoro-p-phenylene group or halogenated arylene group, oxyphenylene group, oxytetrafluorophenylene group, etc. And an iminoarylene group such as an iminophenylene group.
[0024]
Also, R ⁴ Examples of -Ar-R ⁵ Wherein Ar is an arylene group such as an o-, m- or p-phenylene group, an o-, m- or p-tetrafluorophenylene group; ⁵ Is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. More specifically, -C ₆ H ₄ CH ₂ -, -C ₆ H ₄ CH ₂ CH ₂ -, -C ₆ F ₄ CH ₂ And the like.
[0025]
Of these, preferred are 2,4,5-trifluoro-m-phenylene group, 2,4,6-trifluoro-m-phenylene group, 4,5,6-trifluoro-m-phenylene group, , 3,5-trifluoro-p-phenylene group, 2,3,6-trifluoro-p-phenylene group, 3,4,5,6-tetrafluoro-o-phenylene group, 2,4,5,6 -Tetrafluoro-m-phenylene group and 2,3,5,6-tetrafluoro-p-phenylene group, and particularly preferred are 2,4,5,6-tetrafluoro-m-phenylene group and 2,3 , 5,6-tetrafluoro-p-phenylene group.
[0026]
L in the ionic compound (a-1) is selected from a silyl group, a hydroxyl group, a carboxyl group, an amino group, an alkoxy group, an aryloxy group, a phosphino group, and an alkyl group or an aryl group having at least one of these. And is preferably a silyl group or a hydroxyl group. Examples of the silyl group include those represented by the following formula (2).
[0027]
− [Si (Z ¹ Z ² ) -Z ⁶ −] _n SiZ ³ Z ⁴ Z ⁵ (2)
In the above equation (2), Z ¹ , Z ² , Z ³ , Z ⁴ And Z ⁵ Is independently selected from a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, an amide group and a hydrocarbon group having 1 to 20 carbon atoms; ³ , Z ⁴ And Z ⁵ At least one of them is a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group or an amide group. Z ⁶ Is an oxygen atom, an imino group, an alkylene group having 1 to 20 carbon atoms, an arylene group having 1 to 20 carbon atoms, or an oxaalkylene group having 1 to 20 carbon atoms. n is 0 or an integer of 1 to 10.
[0028]
Specific examples of the silyl group include a trihalogenosilyl group such as a trichlorosilyl group, an alkyldihalogenosyl group such as a methyldichlorosilyl group and an ethyldichlorosilyl group, a dimethylchlorosilyl group, and a dialkylhalogenosyl group such as a diethylchlorosilyl group. Group, phenyldichlorosilyl group, aryldihalogenosyl group such as p-tolydichlorosilyl group, diarylhalogenosyl group such as diphenylchlorosilyl group, trialkoxysilyl group such as trimethoxysilyl group, triethoxysilyl group, methyldimethoxy Alkyldialkoxysilyl groups such as silyl group, dialkylalkoxysilyl groups such as dimethylmethoxysilyl group and dimethylethoxysilyl group, and aryldialkoxysilyl groups such as phenyldimethoxysilyl group and tolyldimethoxysilyl group Alkyl-containing silyl groups such as diarylalkoxysilyl groups such as diphenylmethoxysilyl group, ditolylmethoxysilyl group and diphenylethoxysilyl group; triacyloxysilyl groups such as triacetoxysilyl group; and alkyldiacyloxy groups such as methyldiacetoxysilyl group. Silyl group, dialkylacyloxysilyl group such as dimethylacetoxysilyl group, aryldiacyloxysilyl group such as phenyldiacetoxysilyl group, diarylacyloxysilyl group such as diphenylacetoxysilyl group, and alkylhydroxysilyl group such as dimethylhydroxysilyl group. No.
[0029]
Of these, preferred are trichlorosilyl, methyldichlorosilyl, dimethylchlorosilyl, trimethoxysilyl, methyldimethoxysilyl, dimethylmethoxysilyl, triethoxysilyl, methyldiethoxysilyl, dimethylethoxy Silyl group, triacetoxysilyl group, methyldiacetoxysilyl group, dimethylacetoxysilyl group, trihydroxysilyl group, methyldihydroxysilyl group, dimethylhydroxysilyl group, particularly preferred are trichlorosilyl group, methyldichlorosilyl group, dimethyl It is a chlorosilyl group.
[0030]
Examples of the alkyl group having a silyl group include a (trichlorosilyl) methyl group, a (methyldichlorosilyl) methyl group, a (dimethylchlorosilyl) methyl group, a (trimethoxysilyl) methyl group, a (methyldimethoxysilyl) methyl group, and a (dimethyl Silylmethyl groups such as (methoxysilyl) methyl group, (triethoxysilyl) methyl group, (methyldiethoxysilyl) methyl group, (dimethylethoxysilyl) methyl group, (trichlorosilyl) ethyl group, (methyldichlorosilyl) ethyl group A (dimethylchlorosilyl) ethyl group, a (trimethoxysilyl) ethyl group, a (methyldimethoxysilyl) ethyl group, a (dimethylmethoxysilyl) ethyl group, a (triethoxysilyl) ethyl group, a (methyldiethoxysilyl) ethyl group, (Dimethylethoxysilyl) ethyl Such silylethyl group such as and the like.
[0031]
Examples of the aryl group having a silyl group include a (trichlorosilyl) phenyl group, a (methyldichlorosilyl) phenyl group, a (dimethylchlorosilyl) phenyl group, a (trimethoxysilyl) phenyl group, a (methyldimethoxysilyl) phenyl group, Silylphenyl groups such as (dimethylmethoxysilyl) phenyl group, (triethoxysilyl) phenyl group, (methyldiethoxysilyl) phenyl group, (dimethylethoxysilyl) phenyl group, (trichlorosilyl) ethyl group, (methyldichlorosilyl) ) Ethyl, (dimethylchlorosilyl) ethyl, (trimethoxysilyl) ethyl, (methyldimethoxysilyl) ethyl, (dimethylmethoxysilyl) ethyl, (triethoxysilyl) ethyl, (methyldiethoxysilyl) Ethyl group, (dimethi Such silylethyl group such as ethoxy silyl) ethyl group and the like.
[0032]
Examples of the amino group include a dimethylamino group, a diethylamino group, a methylamino group, an ethylamino group, an anilino group, a methylanilino group, a pyrrolidino group, a piperidino group, a piperazino group, an imidazolyl group, a pyridyl group, and a quinolino group. Examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, a butoxy group, a trifluoroethyl group, and an ethylene-1,2-dioxy group. Examples of the aryloxy group include a phenoxy group, a naphthoxy group, a methylphenoxy group, a dimethylphenoxy group, and a pentafluorophenoxy group.
[0033]
In the ionic compound (a-1), a, b and c are 0 or an integer of 1 to 3, d is an integer of 1 to 4, and a + b + c + d = 4. Of these, compounds having d = 1 are preferred.
[0034]
In the ionic compound (a-1), [M ² X _e ] ⁺ Represents a monovalent cation, and M ² Is a (e + 1) -valent cation, and X is any anion. E is 0 or an integer of 1 to 3.
[0035]
M ² As specific examples, proton, triphenylcarbenium ion, triarylcarbenium ion such as tri (p-tolyl) carbenium ion, carbenium ion such as trimethylcarbenium ion, tropylium ion, ferrocenium ion, Ammonium ions such as trimethylammonium ion, tri-n-butylammonium ion and N, N-dimethylanilinium ion, pyridinium ion, pyridinium ion such as 4-methylpyridinium ion, 2-cyanopyridinium ion and 4-cyanopyridinium ion; Oxonium ions such as trimethyloxonium ion and triethyloxonium ion, silylium ions such as trimethylsilylium ion and triethylsilylium ion, lithium, sodium and potassium Um alkali metal ions such as, magnesium, alkaline earth metal ions such as calcium, aluminum, zinc, iron, metal ions such as titanium, or a phosphonium ion.
[0036]
Specific examples of X include halogen ions such as fluorine, chlorine, bromine and iodine, alkoxide or aryloxide ions such as methoxide, ethoxide and phenoxide, acetate ions, propionate ions, butyrate ions and carboxylate ions such as benzoate ions. And the like.
[0037]
In the ionic compound (a-1), e is preferably 0, and thus [M ² X _e ] ⁺ Specific examples thereof include proton, triarylcarbenium ion, triarylcarbenium ion such as tri (p-tolyl) carbenium ion, carbenium ion such as trimethylcarbenium ion, tropylium ion, and ferrocenium. Ions, ammonium ions such as trimethylammonium ion, tri-n-butylammonium ion, N, N-dimethylanilinium ion, pyridinium ions, pyridinium such as 4-methylpyridinium ion, 2-cyanopyridinium ion, 4-cyanopyridinium ion Ions, oxonium ions such as trimethyloxonium ion and triethyloxonium ion, silylium ions such as trimethylsilylium ion and triethylsilylium ion, lithium and sodium Alkali metal ions such as potassium and the like.
[0038]
Among them, particularly preferred are proton, triphenylcarbenium ion, triarylcarbenium ion such as tri- (p-tolyl) carbenium ion, ammonium ion such as triethylammonium ion and tri-n-butylammonium ion; N, N-dimethylanilinium ion, dialkylanilinium ion such as N, N-diethylanilinium ion, trialkyloxonium ion such as trimethyloxonium ion and triethyloxonium ion, trimethylsilylium ion, triethylsilylium ion And the like. Most preferred of these are dialkylanilinium and trialkylammonium ions.
[0039]
Specific examples of the ionic compound (a-1) that can be suitably used in the present invention include those having a halogenated silyl group.
N, N-dimethylanilinium [4- (chlorodimethylsilyl) -2,3,5,6-tetrafluorophenyl] tris (pentafluorophenyl) borate,
N, N-dimethylanilinium [4- (methyldichlorosilyl) -2,3,5,6-tetrafluorophenyl] tris (pentafluorophenyl) borate;
N, N-dimethylanilinium (4-trichlorosilyl-2,3,5,6-tetrafluorophenyl) tris (pentafluorophenyl) borate,
N, N-dimethylanilinium [4- (chlorodiethylsilyl) -2,3,5,6-tetrafluorophenyl] tris (pentafluorophenyl) borate;
N, N-dimethylanilinium [4- (ethyldichlorosilyl) -2,3,5,6-tetrafluorophenyl] tris (pentafluorophenyl) borate,
Tri-n-butylammonium [4- (chlorodimethylsilyl) -2,3,5,6-tetrafluorophenyl] tris (pentafluorophenyl) borate,
Tri-n-butylammonium [4- (methyldichlorosilyl) -2,3,5,6-tetrafluorophenyl] tris (pentafluorophenyl) borate,
Tri-n-butylammonium (4-trichlorosilyl-2,3,5,6-tetrafluorophenyl) tris (pentafluorophenyl) borate,
Tri-n-butylammonium [4- (chlorodiethylsilyl) -2,3,5,6-tetrafluorophenyl] tris (pentafluorophenyl) borate,
Tri-n-butylammonium [4- (ethyldichlorosilyl) -2,3,5,6-tetrafluorophenyl] tris (pentafluorophenyl) borate,
Triphenylcarbenium [4- (chlorodimethylsilyl) -2,3,5,6-tetrafluorophenyl] tris (pentafluorophenyl) borate,
Triphenylcarbenium [4- (methyldichlorosilyl) -2,3,5,6-tetrafluorophenyl] tris (pentafluorophenyl) borate,
Triphenylcarbenium (4-trichlorosilyl-2,3,5,6-tetrafluorophenyl) tris (pentafluorophenyl) borate,
Triphenylcarbenium [4- (chlorodiethylsilyl) -2,3,5,6-tetrafluorophenyl] tris (pentafluorophenyl) borate,
Triphenylcarbenium [4- (ethyldichlorosilyl) -2,3,5,6-tetrafluorophenyl] tris (pentafluorophenyl) borate
and so on.
[0040]
Also,
N, N-dimethylanilinium [4- (chlorodimethylsilyl) -phenyl] tris (pentafluorophenyl) borate,
N, N-dimethylanilinium [4- (methyldichlorosilyl) -phenyl] tris (pentafluorophenyl) borate;
N, N-dimethylanilinium (4-trichlorosilyl-phenyl) tris (pentafluorophenyl) borate,
N, N-dimethylanilinium [4- (chlorodiethylsilyl) -phenyl] tris (pentafluorophenyl) borate,
N, N-dimethylanilinium [4- (ethyldichlorosilyl) -phenyl] tris (pentafluorophenyl) borate;
Tri-n-butylammonium [4- (chlorodimethylsilyl) -phenyl] tris (pentafluorophenyl) borate,
Tri-n-butylammonium [4- (methyldichlorosilyl) -phenyl] tris (pentafluorophenyl) borate,
Tri-n-butylammonium (4-trichlorosilyl-phenyl) tris (pentafluorophenyl) borate,
Tri-n-butylammonium [4- (chlorodiethylsilyl) -phenyl] tris (pentafluorophenyl) borate,
Tri-n-butylammonium [4- (ethyldichlorosilyl) -phenyl] tris (pentafluorophenyl) borate,
Triphenylcarbenium [4- (chlorodimethylsilyl) -phenyl] tris (pentafluorophenyl) borate,
Triphenylcarbenium [4- (methyldichlorosilyl) -phenyl] tris (pentafluorophenyl) borate,
Triphenylcarbenium (4-trichlorosilyl-phenyl) tris (pentafluorophenyl) borate,
Triphenylcarbenium [4- (chlorodiethylsilyl) -phenyl] tris (pentafluorophenyl) borate,
Triphenylcarbenium [4- (ethyldichlorosilyl) -phenyl] tris (pentafluorophenyl) borate
And the like.
[0041]
Moreover,
N, N-dimethylanilinium [4- (chlorodimethylsilyl) -phenyl] tris [3,5-bis (trifluoromethyl) phenyl] borate;
N, N-dimethylanilinium [4- (methyldichlorosilyl) -phenyl] tris [3,5-bis (trifluoromethyl) phenyl] borate;
N, N-dimethylanilinium (4-trichlorosilylphenyl) tris [3,5-bis (trifluoromethyl) phenyl] borate,
N, N-dimethylanilinium [4- (chlorodiethylsilyl) -phenyl] tris [3,5-bis (trifluoromethyl) phenyl] borate;
N, N-dimethylanilinium [4- (ethyldichlorosilyl) -phenyl] tris [3,5-bis (trifluoromethyl) phenyl] borate;
Tri-n-butylammonium [4- (chlorodimethylsilyl) -phenyl] tris [3,5-bis (trifluoromethyl) phenyl] borate,
Tri-n-butylammonium [4- (methyldichlorosilyl) -phenyl] tris [3,5-bis (trifluoromethyl) phenyl] borate,
Tri-n-butylammonium (4-trichlorosilylphenyl) tris [3,5-bis (trifluoromethyl) phenyl] borate,
Tri-n-butylammonium [4- (chlorodiethylsilyl) -phenyl] tris [3,5-bis (trifluoromethyl) phenyl] borate,
Tri-n-butylammonium [4- (ethyldichlorosilyl) -phenyl] tris [3,5-bis (trifluoromethyl) phenyl] borate,
Triphenylcarbenium [4- (chlorodimethylsilyl) -phenyl] tris [3,5-bis (trifluoromethyl) phenyl] borate,
Triphenylcarbenium [4- (methyldichlorosilyl) -phenyl] tris [3,5-bis (trifluoromethyl) phenyl] borate,
Triphenylcarbenium (4-trichlorosilyl-phenyl) tris [3,5-bis (trifluoromethyl) phenyl] borate,
Triphenylcarbenium [4- (chlorodiethylsilyl) -phenyl] tris [3,5-bis (trifluoromethyl) phenyl] borate,
Triphenylcarbenium [4- (ethyldichlorosilyl) -phenyl] tris [3,5-bis (trifluoromethyl) phenyl] borate
Are also exemplified.
[0042]
Specific examples of the ionic compound (a-1) that can be suitably used in the present invention include those having an alkoxysilyl group.
N, N-dimethylanilinium [4- (methoxydimethylsilyl) -2,3,5,6-tetrafluorophenyl] tris (pentafluorophenyl) borate, N, N-dimethylanilinium [4- (methyldimethoxysilyl) ) -2,3,5,6-tetrafluorophenyl] tris (pentafluorophenyl) borate, N, N-dimethylanilinium (4-methoxylyl-2,3,5,6-tetrafluorophenyl) tris (pentafluorophenyl) Phenyl) borate,
N, N-dimethylanilinium [4- (methoxydiethylsilyl) -2,3,5,6-tetrafluorophenyl] tris (pentafluorophenyl) borate,
N, N-dimethylanilinium [4- (ethyldimethoxysilyl) -2,3,5,6-tetrafluorophenyl] tris (pentafluorophenyl) borate,
Tri-n-butylammonium [4- (ethoxydimethylsilyl) -2,3,5,6-tetrafluorophenyl] tris (pentafluorophenyl) borate,
Tri-n-butylammonium [4- (methyldiethoxysilyl) -2,3,5,6-tetrafluorophenyl] tris (pentafluorophenyl) borate,
Tri-n-butylammonium (4-triethoxysilyl-2,3,5,6-tetrafluorophenyl) tris (pentafluorophenyl) borate,
Tri-n-butylammonium [4- (ethoxydiethylsilyl) -2,3,5,6-tetrafluorophenyl] tris (pentafluorophenyl) borate,
Tri-n-butylammonium [4- (ethyldiethoxysilyl) -2,3,5,6-tetrafluorophenyl] tris (pentafluorophenyl) borate,
Triphenylcarbenium [4- (ethoxydimethylsilyl) -2,3,5,6-tetrafluorophenyl] tris (pentafluorophenyl) borate,
Triphenylcarbenium [4- (methyldiethoxysilyl) -2,3,5,6-tetrafluorophenyl] tris (pentafluorophenyl) borate,
Triphenylcarbenium (4-triethoxysilyl-2,3,5,6-tetrafluorophenyl) tris (pentafluorophenyl) borate,
Triphenylcarbenium [4- (ethoxydiethylsilyl) -2,3,5,6-tetrafluorophenyl] tris (pentafluorophenyl) borate,
Triphenylcarbenium [4- (ethyldiethoxysilyl) -2,3,5,6-tetrafluorophenyl] tris (pentafluorophenyl) borate
and so on.
[0043]
Specific examples of the ionic compound (a-1) which can be suitably used in the present invention include those having a group other than a halogenated silyl group and an alkoxysilyl group.
N, N-dimethylanilinium (4-hydroxy-2,3,5,6-tetrafluorophenyl) tris (pentafluorophenyl) borate,
N, N-dimethylanilinium (4-hydroxyphenyl) tris (pentafluorophenyl) borate,
Tri-n-butylammonium (4-hydroxy-2,3,5,6-tetrafluorophenyl) tris (pentafluorophenyl) borate,
Tri-n-butylammonium (4-hydroxyphenyl) tris (pentafluorophenyl) borate
and so on.
[0044]
Examples of the fine particle carrier used in (A) in the present invention include metal oxides, metal halides, metal hydroxides, metal alkoxides, carbonates, sulfates, acetates, silicates, and organic polymer compounds. Can be These can be used alone or in combination of two or more as required. These may be treated with an organoaluminum, an organosilicon compound, or the like.
[0045]
Examples of the metal oxide include silica, alumina, titania, magnesia, zirconia, calcia, and zinc oxide. Examples of the metal halide include magnesium chloride, calcium chloride, barium chloride, sodium chloride and the like. Examples of the metal hydroxide include aluminum hydroxide and magnesium hydroxide. Examples of the metal alkoxide include magnesium ethoxide and magnesium methoxide. Examples of the carbonate include calcium carbonate, basic calcium carbonate, magnesium carbonate, basic magnesium carbonate, barium carbonate, and the like. Examples of the sulfate include calcium sulfate, magnesium sulfate, barium sulfate, and the like. Examples of the acetate include calcium acetate and magnesium acetate. Examples of the silicate include magnesium silicate such as mica and talc, calcium silicate, and sodium silicate. Among them, preferred are magnesium silicates such as silica, alumina, mica and talc, and silicates such as calcium silicate, aluminum silicate and sodium silicate.
[0046]
Examples of the organic polymer compound include polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl ester copolymer, polyolefins such as partially or completely saponified ethylene-vinyl ester copolymers, and modified products thereof, Thermoplastic resins such as polystyrene, polystyrene having a functional group such as a hydroxyl group, cross-linked polystyrene, cross-linked polystyrene having a functional group such as a hydroxyl group, polyamide, polycarbonate, polyester, and the like, and heat of a phenol resin, an epoxy resin, a urea resin, a melamine resin, etc. Curable resin and the like can be mentioned.
[0047]
Of these, preferred as (a-2) are metal oxides such as silica and alumina; metal halides such as magnesium chloride; metal hydroxides such as aluminum hydroxide; silicates such as aluminum silicate; A polymer compound having a polar group such as a carboxyl group, an amino group or an amide group is most preferable, and the most preferable are metal oxides such as silica and alumina, silicates such as aluminum silicate, and metal hydroxides such as aluminum hydroxide. Having a hydroxyl group of
[0048]
The average particle size of these fine particle carriers is not particularly limited, but is usually preferably in the range of 0.1 to 2,000 μm, preferably 1 to 1,000 μm, more preferably 10 to 500 μm, and further preferably The range is from 15 to 300 μm, more preferably from 20 to 200 μm, particularly preferably from 25 to 120 μm, and most preferably from 30 to 80 μm.
[0049]
The specific surface area is not particularly limited, but is usually 0.1 to 2,000 m. ² / G, preferably from 10 to 1,500 m ² / G, more preferably 100 to 1,020 m ² / G, more preferably 200 to 1000 m ² / G, even more preferably 300 to 1000 m ² / G, particularly preferably 400 to 900 m ² / G, most preferably 500-900 m ² / G.
[0050]
The contact between the non-coordinating ion-containing compound (a-1) and the particulate carrier (a-2) can be performed by any method, and even when the non-coordinating ion-containing compound (a-1) is directly contacted in the absence of an organic solvent. The contact is preferably performed in an organic solvent. Examples of the organic solvent used herein include aliphatic hydrocarbons such as pentane and hexane; aromatic hydrocarbons such as benzene and toluene; halogenated hydrocarbons such as methylene chloride and chlorobenzene; ethers such as diethyl ether and tetrahydrofuran; Amides such as N, N-dimethylformamide and N-methylpyrrolidone, alcohols such as methanol, ethanol, propanol and n-butanol, and mixtures thereof.
[0051]
The contact between the non-coordinating ion-containing compound (a-1) and the particulate carrier (a-2) can be carried out at any temperature in consideration of the organic solvent used and other conditions. It is preferable to carry out in the range of 80 ° C to 300 ° C. A preferred contact temperature range is from -50C to 200C, and a more preferred range is from 0C to 150C.
[0052]
The amount of the non-coordinating ion-containing compound (a-1) to be used in the particulate carrier (a-2) is not particularly limited, but is usually (a-1) per 100 parts by weight of (a-2). ) Is preferably in the range of 0.0001 to 1,000,000 parts by weight. When the amount of (a-1) used is increased, the polymerization activity of the catalyst tends to be improved. However, in consideration of the balance between the polymerization activity and the production cost, the amount of (a-1) used is 100 parts of the fine particle carrier (a-2). It is preferably in the range of 0.1 to 10,000 parts by weight, more preferably in the range of 1 to 1,000 parts by weight with respect to parts by weight.
[0053]
The component (A) in the present invention preferably has a non-coordinating ion-containing compound content of usually from 0.010 to 0.50 mmol / g, preferably from 0 to 0.50 mmol / g, per 1 g of (A). 0.030-0.40 mmol / g, more preferably 0.050-0.40 mmol / g, still more preferably 0.055-0.40 mmol / g, and even more preferably 0.060-0.35 mmol. / G, particularly preferably 0.065-0.35 mmol / g, most preferably 0.070-0.30 mmol / g. If the content of the non-coordinating ion-containing compound is less than the above, the polymerization activity per catalyst may decrease, and if it exceeds the above, the polymerization activity per the non-coordinating ion-containing compound may decrease.
[0054]
In the case where a component (a-2) having a polar group such as a hydroxyl group is used as the component (A) in the present invention, a polar group such as a hydroxyl group, a carboxyl group, an amino group, or an amide group derived from the fine particle carrier is used. The groups can be reduced by heat treatment or chemical treatment. Specifically, there are a method of preparing the component (A) using a fine particle carrier in which the polar group content is adjusted by performing these treatments, and a method of preparing the component (A) and then performing these treatments.
[0055]
The heat treatment is performed by heating the fine particle carrier or the component (A) at a temperature of 50 ° C or higher, preferably 100 to 1,000 ° C, more preferably 100 to 800 ° C under normal pressure or reduced pressure. Is good.
[0056]
The chemical treatment is preferably performed by contacting with a compound capable of reacting with a polar group derived from the fine particle carrier, and specifically, an alkylating agent such as methyl iodide and ethyl iodide, an acylating agent, and trimethylchlorosilane. , Phenyldimethylchlorosilane, diphenyldichlorosilane, hexamethyldisilazane, etc .; Specifically, this treatment is carried out after or simultaneously with the contact of the non-coordinating ion-containing compound (a-1) with the particulate carrier (a-2). It is performed by contacting with at least one or more of an agent, a stannylating agent, and a gel-milling agent.
[0057]
As the metallocene compound (B) that can be used in the present invention, known compounds can be used without any limitation. For example, biscyclopentadienyl zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (1 , 2-Dimethylcyclopentadienyl) zirconium dichloride, bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, bis (ethylcyclopentadienyl) zirconium dichloride, bis (n-propylcyclopentadienyl) zirconium dichloride , Bis (n-butylcyclopentadienyl) zirconium dichloride, bis (1,2,3-trimethylcyclopentadienyl) zirconium dichloride, bis (1,2,4-trimethylcyclopentadienyl) ) Zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, (methylcyclopentadienyl) (indenyl) zirconium dichloride, (3-t-butylcyclopentadienyl) (1-indenyl) zirconium dichloride, (t -Butylamide) (tetramethylcyclopentadienyl) dimethylsilanetitanium dichloride and the like.
[0058]
When a propylene polymer is produced, it is preferable to polymerize propylene in a stereoregular manner. More specifically, bis (2,3-dimethylcyclopentadienyl) dimethylsilanezirconium dichloride and bis ( 2,4-dimethylcyclopentadienyl) dimethylsilane zirconium dichloride, bis (2,3,5-trimethylcyclopentadienyl) dimethylsilane zirconium dichloride, (methylcyclopentadienyl) (1-indenyl) dimethylsilane zirconium dichloride , (3-t-butylcyclopentadienyl) (1-indenyl) dimethylsilanezirconium dichloride.
[0059]
Further, (3-t-butylcyclopentadienyl) [4-t-butyl- (1-indenyl)] dimethylsilanezirconium dichloride, (methylcyclopentadienyl) (9-fluorenyl) dimethylsilanezirconium dichloride, (3 -T-butylcyclopentadienyl) (9-fluorenyl) dimethylsilane zirconium dichloride, bis (1-indenyl) dimethylsilane zirconium dichloride, bis (2-methyl-1-indenyl) dimethylsilane zirconium dichloride, bis (2,4 , 7-Trimethyl-1-indenyl) dimethylsilanezirconium dichloride, bis (2,4-dimethyl-1-indenyl) dimethylsilanezirconium dichloride, bis (2-ethyl-1-indenyl) dimethylsilanezirco Umujikuroraido, and bis (2-i-propyl-1-indenyl) dimethylsilane zirconium dichloride can also be used.
[0060]
Further, metallocene compounds having a structure in which a ring is further condensed to an indenyl skeleton described in JP-A-6-184179, JP-A-6-345809, and the like, that is, bis (2-methyl-4,5-benzo- 1-indenyl) dimethylsilane zirconium dichloride, bis (2-methyl-α-acenaphth-1-indenyl) dimethylsilanezirconium dichloride, bis (2-methyl-4,5-benzo-1-indenyl) methylphenylsilanezirconium dichloride, Bis (2-methyl-α-acenaphth-1-indenyl) methylphenylsilanezirconium dichloride, 1,2-bis (2-methyl-4,5-benzo-1-indenyl) ethanezirconium dichloride, bis (4,5- Benzo-1-indenyl) dimethylsilane Zirconium dichloride can also be used.
[0061]
Further, metallocene compounds having an aryl group at the 4-position of the indenyl skeleton, that is, bis (2-methyl-4-phenyl-1) described in JP-A-6-100579 and JP-A-9-176222. -Indenyl) dimethylsilane zirconium dichloride, (2-methyl-4-phenyl-1-indenyl) dimethylsilanezirconium dichloride, bis [2-methyl-4- (1-naphthyl) -1-indenyl] dimethylsilanezirconium dichloride, bis [2-methyl-4- (2-naphthyl) -1-indenyl] dimethylsilane zirconium dichloride, bis [2-methyl-4- (9-anthracenyl) -1-indenyl] dimethylsilane zirconium dichloride, bis [2-methyl -4- (9-phenanthryl)- -Indenyl] dimethylsilane zirconium dichloride, bis [2-methyl-4- (3,5-di-i-propyl-phenyl) -6-i-propyl-1-indenyl] dimethylsilanezirconium dichloride, bis (2-methyl 4-phenyl-6-i-propyl-1-indenyl) dimethylsilanezirconium dichloride and the like can also be used.
[0062]
Further, a metallocene compound having an azulene skeleton described in JP-A-10-226712 and JP-A-10-279588, that is, bis (2-methyl-4-phenyl-4-hydro-1-azulenyl) dimethylsilane Zirconium dichloride, bis (2-ethyl-4-phenyl-4-hydro-1-azulenyl) dimethylsilane zirconium dichloride, bis [2-methyl-4- (chlorophenyl) -4-hydro-1-azulenyl] dimethylsilane zirconium dichloride Bis [2-methyl-4- (fluorophenyl) -4-hydro-1-azulenyl] dimethylsilanezirconium dichloride, bis (2-methyl-4-phenyl-4-hydro-1-azulenyl) (chloromethyl) methyl Silane zirconium dichloride, etc. It is possible to use.
[0063]
Further, bis [2-methyl- (η ⁵ -1-indenyl)] methylphenylsilane zirconium dichloride, 1,2-bis (η ⁵ -1-indenyl) ethane zirconium dichloride, 1,2-bis [2-methyl- (η ⁵ -1-indenyl)] ethane zirconium dichloride, 1,2-bis [2,4-dimethyl- (η ⁵ -1-indenyl)] ethane zirconium dichloride, 1,2-bis [2,4,7-trimethyl- (η ⁵ -1-indenyl)] ethane zirconium dichloride, 1,2-bis [2-ethyl- (η ⁵ -1-indenyl)] ethane zirconium dichloride, 1,2-bis [2-n-propyl- (η ⁵ -1-indenyl)] ethane zirconium dichloride, 1- [2-ethyl- (η ⁵ -1-indenyl)]-2- [2-methyl- (η ⁵ -1-indenyl)] ethanezirconium dichloride, 1,2-bis (η ⁵ -9-fluorenyl) ethane zirconium dichloride, 2- (3-t-butylcyclopentadienyl) -2- (η ⁵ -1-indenyl) propane zirconium dichloride, 2- (3-t-butylcyclopentadienyl) -2- [4-t-butyl- (η ⁵ -1-indenyl)] propane zirconium dichloride, 2- (3-methylcyclopentadienyl) -2- (η ⁵ -9-fluorenyl) propane zirconium dichloride, 2- (3-t-butylcyclopentadienyl) -2- (η ⁵ (-9-fluorenyl) propane zirconium dichloride and the like can be used.
[0064]
Among them, those having an aryl group at the 4-position of the indenyl skeleton described in JP-A-6-100579 and JP-A-9-176222, JP-A-6-184179 and JP-A-6-345809. Metallocene compounds having a structure in which a ring is further condensed to an indenyl skeleton described in a gazette, and a metallocene compound having an azulene skeleton described in JP-A-10-226712 and JP-A-10-279588 are preferable, In particular, bis [2-methyl-4,5-benzo (η ⁵ -1-indenyl)] dimethylsilane zirconium dichloride, bis [2-methyl-4-phenyl- (η ⁵ -1-indenyl)] dimethylsilane zirconium dichloride, bis [2-methyl-4- (1-naphthyl)-(η ⁵ -1-indenyl)] dimethylsilanezirconium dichloride and bis (2-methyl-4-phenyl-4-hydro-1-azulenyl) dimethylsilanezirconium dichloride are preferred.
[0065]
In addition, zirconium of these metallocene compounds is replaced with another metal such as titanium or hafnium, or a chlorine atom is replaced with another halogen, a hydrogen atom, an amide group, an alkoxy group, a hydrocarbon group such as a methyl group or a benzyl group. The alternative can be used without any restrictions.
[0066]
The amount of (B) used relative to (A) is such that the non-coordinating ion-containing compound in (A) is 0.05 to 100 mol per 1 mol of a transition metal such as zirconium contained in (B). It is preferably in the range of 0.1 to 50 mol, more preferably 0.3 to 20 mol, particularly preferably 0.5 to 10 mol.
[0067]
The organometallic compound (C) in the present invention is preferably selected from an organic aluminum compound, an organic lithium compound, an organic zinc compound, and an organic magnesium compound, and a plurality of these may be used in combination. Preferred among these are organoaluminum compounds.
[0068]
As the organoaluminum compound, known compounds can be used. For example, trialkylaluminum such as trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride , Methyl aluminum dichloride, ethyl aluminum dichloride, dialkyl aluminum halide such as monoisobutyl aluminum dichloride and the like, alkyl aluminum dihalide, dialkyl aluminum hydride such as diisobutyl aluminum hydride, diethyl aluminum methoxide, dialkyl aluminum alkoxide such as diethyl aluminum phenoxide or aryl oxide, G Such alkenyl aluminum Nim such isoprenyl aluminum.
[0069]
Of these, trialkylaluminum is preferred, and more preferably those having alkyl having 1 to 10 carbon atoms. Specifically, triethyl aluminum, tri-n-propyl aluminum, triisopropyl aluminum, tri-n-butyl aluminum, triisobutyl aluminum, tri-n-hexyl aluminum, tri-n-octyl aluminum, tri-n-decyl aluminum , Triisohexyl aluminum, triisooctyl aluminum, etc., and particularly preferably triisobutyl aluminum, tri-n-butyl aluminum, tri-n-hexyl aluminum, tri-n-octyl aluminum, tri-n-decyl aluminum, tri-n-decyl aluminum, Isohexyl aluminum and triisooctyl aluminum, most preferably triisobutyl aluminum, tri-n-butyl aluminum, tri-n-hexyl aluminum and tri-n- A Chi le aluminum, it is possible to obtain a propylene polymer with particularly high polymerization activity when using them. These can be used alone or in combination of two or more as required.
[0070]
Examples of the organic lithium compound include aryl lithium such as phenyl lithium, and alkyl lithium such as methyl lithium, n-butyl lithium, isobutyl lithium, s-butyl lithium, and t-butyl lithium. Examples of the organic zinc compound include dimethyl zinc and diethyl zinc, and examples of the organic magnesium include dialkyl magnesium such as di-n-butylmagnesium, di-n-hexylmagnesium, and n-butylethylmagnesium, methylmagnesium bromide, and ethylmagnesium bromide. , N-propylmagnesium bromide, isopropylmagnesium bromide, n-butylmagnesium chloride, isobutylmagnesium chloride, s-butylmagnesium chloride, t-butylmagnesium chloride, phenylmagnesium bromide, and replacing their chlorine and bromine atoms with other halogens And alkyl magnesium halides.
[0071]
In the present invention, the amount of (C) used is not particularly limited, but is generally in the range of 10 to 100,000 mol per 1 mol of the transition metal such as zirconium contained in (B). Well, preferably 20 to 70,000 moles, more preferably 25 to 50,000 moles, still more preferably 50 to 30,000 moles, still more preferably 70 to 30,000 moles, and still more preferably 100 to 30,000 moles. Moles, particularly preferably in the range from 150 to 20,000 moles, most preferably from 200 to 10,000 moles.
[0072]
The polymerization catalyst used in the present invention comprises the above (A), (B) and (C). The preparation method is not particularly limited, and it can be prepared by contacting in any method and in any order. That is, a method of simultaneously contacting each of the catalyst components (A), (B) and (C) and a method of sequentially contacting each of the catalyst components are possible. The number of times of contact is also arbitrary, and each component can be contacted a plurality of times.
[0073]
The contact of each of the components can be performed in the presence or absence of any solvent, such as propane, butane, pentane, hexane, heptane, octane, aliphatic hydrocarbons such as decane, cyclopentane, Alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene and dichlorobenzene And ethers such as diethyl ether and tetrahydrofuran. Among these, aromatic hydrocarbons and halogenated hydrocarbons are preferred, and toluene, xylene, dichloromethane and chloroform are particularly preferred. Further, two or more hydrocarbon solvents may be used in combination. Furthermore, if the components are contacted sequentially, different solvents can be used in each contacting step.
[0074]
The contact temperature varies depending on the combination of components to be contacted, but may be usually in the range of -70 ° C to 200 ° C, preferably in the range of -50 ° C to 150 ° C, particularly preferably in the range of -20 ° C to 120 ° C. is there. In addition, the contact time is optional and is usually in the range of 0.5 to 600 minutes, preferably in the range of 1 to 300 minutes, and more preferably in the range of 3 to 120 minutes. When the components are sequentially contacted, the contact can be performed at different temperatures and times in each contacting step.
[0075]
Next, the nonionic surfactant (D) used in the present invention will be described. In the present invention, as (D), any known nonionic surfactant can be used without any limitation. These may be used in combination of two or more. In the present invention, when an ionic surfactant is used as (D), the polymerization activity may be significantly reduced, fouling may occur, or a polymer having a low bulk density may be produced.
[0076]
Examples of the (D) nonionic surfactant include (D-1) a polyalkylene oxide, (D-2) an etherified product of a polyalkylene oxide, (D-3) a carboxylic acid ester of a polyalkylene oxide, and (D-4). ) Polyoxyalkylenealkylamines, (D-5) alkyldiethanolamines and (D-6) higher aliphatic amides are preferred.
[0077]
As the polyalkylene oxide (D-1), any conventionally known polyalkylene oxide can be used without any limitation. Suitable as (D-1) polyalkylene oxide are HO- (CH ₂ CH ₂ O) _m Polyethylene oxide represented by —H, HO— ｛CH ₂ CH (CH ₃ ) O｝ _l Diol-type polypropylene oxide represented by -H and R ⁶ OCH ₂ CH (OR ⁷ ) CH ₂ OR ⁸ (R ⁶ =-｛CH ₂ CH (CH ₃ ) O｝ _p1 -H, R ⁷ =-｛CH ₂ CH (CH ₃ ) O｝ _p2 -H, R ⁸ =-｛CH ₂ CH (CH ₃ ) O｝ _p3 -H) is a triol-type polypropylene oxide. M indicating the average degree of polymerization of the polyethylene oxide is preferably in the range of 2 to 40, preferably 3 to 30, and more preferably 4 to 20, and 1 indicating the average degree of polymerization of the diol-type polypropylene oxide is 2 to 80, preferably 3 to 70, more preferably 4 to 60, and p1, p2 and p3 indicating the average polymerization degree of the triol type polypropylene oxide may be the same or different. , Respectively, preferably in the range of 2 to 80, preferably 2 to 70, more preferably 2 to 60.
[0078]
Examples of (D-1) polyalkylene oxide include, in addition to the above polyethylene oxide and polypropylene oxide, for example, polyalkylene oxide in which ethylene oxide and propylene oxide are randomly copolymerized, polytetramethylene oxide, polyneopenthylene Oxide, polyhexylene oxide and the like are also preferably used. Further, (D-1) a polyoxyalkylene polyol obtained by adding an alkylene oxide to a polyhydric alcohol such as glycerin or trimethylolpropane is preferable as the polyalkylene oxide. The polyoxyalkylene polyol is obtained by adding 2 to 30 mol, preferably 3 to 20 mol, more preferably 4 to 8 mol of ethylene oxide to one functional group of the polyhydric alcohol, or polyhydric alcohol. It is desirable that propylene oxide is added in an amount of 2 to 30 mol, preferably 3 to 20 mol, more preferably 4 to 8 mol, based on 1 functional group.
[0079]
As the (D-1) polyalkylene oxide, a compound represented by the general formula HO- (CH ₂ CH ₂ O) _q1 − ｛CH ₂ CH (CH ₃ ) O｝ _q2 − (CH ₂ CH ₂ O) _q3 A polyethylene oxide-polypropylene oxide-polyethylene oxide block represented by -H can also be preferably used. In the above general formula, (CH ₂ CH ₂ Q1 indicating the average chain length of the oxyethylene unit represented by O) is preferably in the range of 1 to 30, preferably 1 to 20, more preferably 1 to 10, and q3 is 1 to 30, preferably 1 -20, more preferably 1-10. ₂ CH (CH ₃ It is desirable that q2 indicating the average chain length of the oxypropylene unit represented by O) is in the range of 2 to 50, preferably 3 to 45, more preferably 4 to 40.
[0080]
Further, as a suitable compound as the (D-1) polyalkylene oxide, a compound represented by the general formula HO- ｛CH ₂ CH (CH ₃ ) O｝ _r1 − (CH ₂ CH ₂ O) _r2 − ｛CH ₂ CH (CH ₃ ) O｝ _r3 And a polypropylene oxide-polyethylene oxide-polypropylene oxide block represented by -H. In the above general formula, (CH ₂ CH ₂ R2, which represents the average chain length of oxyethylene units represented by O), is preferably in the range of 1 to 50, preferably 1 to 40, more preferably 2 to 30; ₂ CH (CH ₃ R) The average chain length of the oxypropylene unit represented by O 表 is preferably in the range of 2 to 30, preferably 3 to 25, more preferably 4 to 20, and r3 is 2 to 30, preferably It is desirable to be in the range of 3 to 25, more preferably 4 to 20.
[0081]
The etherified product of (D-2) polyalkylene oxide is generally used as a nonionic surfactant, and any conventionally known one can be used without any limitation. Of these, preferred is-(CH ₂ CH ₂ O) _x -H or-｛CH ₂ CH (CH ₃ ) O｝ _y Examples thereof include an alkyl ether or aryl ether compound having -H, and specific examples thereof include the following compounds.
[0082]
That is, the general formula R ⁹ O (CH ₂ CH ₂ O) _x -H, a polyoxyethylene ether represented by the general formula R ⁹ O ｛CH ₂ CH (CH ₃ ) O｝ _y -H, a polyoxypropylene ether represented by the general formula R ⁹ C ₆ H ₄ O (CH ₂ CH ₂ O) _x A polyoxyethylene aryl ether represented by the general formula R ⁹ C ₆ H ₄ O ｛CH ₂ CH (CH ₃ ) O｝ _y A polyoxypropylene aryl ether represented by the general formula (R ⁹ ) ₂ CHO (CH ₂ CH ₂ O) _x A polyoxyethylene ether represented by the general formula (R ⁹ ) ₂ CHO ｛CH ₂ CH (CH ₃ ) O｝ _x A polyoxypropylene ether represented by the general formula (R ⁹ ) ₃ CO (CH ₂ CH ₂ O) _x A polyoxyethylene ether represented by the general formula (R ⁹ ) ₃ CO ｛CH ₂ CH (CH ₃ ) O｝ _y And polyoxypropylene ether represented by -H.
[0083]
In the above general formula, R ⁹ Is selected from an alkyl group, an alkenyl group and an alkadienyl group having 1 to 30 carbon atoms, preferably an alkyl group and an alkenyl group having 6 to 20 carbon atoms, more preferably an alkyl group having 8 to 20 carbon atoms. It is. Examples of the alkyl group include a methyl group, an ethyl group, a hexyl group, an octyl group, a decyl group, a lauryl group, a cetyl group, a myristyl group, a palmityl group, and a stearyl group. Examples of the alkenyl group include an allyl group, a methallyl group, an isopropenyl group, an undecylenyl group, and an oleyl group.
[0084]
Also, (CH ₂ CH ₂ X, which represents the average chain length of the oxyethylene unit represented by O), is preferably in the range of 2 to 40, preferably 3 to 30, more preferably 4 to 20, ₂ CH (CH ₃ It is desirable that y indicating the average chain length of the oxypropylene unit represented by O} is 2 to 80, preferably 3 to 70, and more preferably 4 to 60.
[0085]
Among the ether compounds represented by the above general formula, polyoxypropylene lauryl ether, polyoxypropylene cetyl ether, polyoxypropylene stearyl ether, polyoxypropylene octyl ether, polyoxypropylene nonyl phenyl ether, polyoxypropylene palmityl ether , Polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene octyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene palmityl ether, and the like. Are preferable, and the compound whose repeating unit number of an oxyethylene unit is 4-10 is preferable.
[0086]
As the polyalkylene oxide alkyl ether, in addition to the above-described polyethylene oxide alkyl ether and polypropylene oxide alkyl ether, the polyalkylene oxide portion is, for example, a polyalkylene oxide or a random copolymer of ethylene oxide and propylene oxide or a block copolymer. Alkylene oxide alkyl ether compounds are also preferably used.
[0087]
(D-3) The carboxylic acid ester of polyalkylene oxide is generally used as a nonionic surfactant, and any conventionally known polyalkylene oxide ester can be used without any limitation. Preferred as (D-3) polyalkylene oxide ester are-(CH ₂ CH ₂ O) _x -H or-｛CH ₂ CH (CH ₃ ) O｝ _y -H, an ester compound having the general formula R ¹⁰ COO (CH ₂ CH ₂ O) _x A polyoxyethylene ester represented by the general formula R ¹⁰ COO @ CH ₂ CH (CH ₃ ) O｝ _y Compounds such as polyoxypropylene esters represented by -H can be exemplified.
[0088]
In the above general formula, R ¹⁰ Is selected from an alkyl group having 1 to 30 carbon atoms, an alkenyl group and an alkadienyl group, preferably an alkyl group having 5 to 19 carbon atoms and an alkadienyl group, more preferably an alkyl group having 7 to 19 carbon atoms. It is. In the above general formula, R ¹⁰ Examples of the acyl group represented by COO- include a hexanoyl group, an octanoyl group, a decanoyl group, a lauroyl group, a cetanoyl group, a myristoyl group, a palmitoyl group, and a stearoyl group. Also, (CH ₂ CH ₂ X, which represents the average chain length of the oxyethylene unit represented by O), is preferably in the range of 2 to 40, preferably 3 to 30, more preferably 4 to 20, ₂ CH (CH ₃ It is desirable that y indicating the average chain length of the oxypropylene unit represented by O} is 2 to 80, preferably 3 to 70, and more preferably 4 to 60.
[0089]
Among the above ester compounds, polyoxyethylene monolaurate, polyoxyethylene monostearate, polyoxyethylene monooctanoate, polyoxyethylene monopalmitate, polyoxyethylene monooleate, polyoxypropylene monolaurate , Polyoxypropylene monostearate, polyoxypropylene monopalmitate, polyoxypropylene monooleate, and the like are preferable, and in particular, a compound having 4 to 10 repeating units of oxyethylene units and a compound having 4 repeating units of oxypropylene units Are preferred.
[0090]
(D-3) As the carboxylic acid ester of polyalkylene oxide, in addition to the above-described polyethylene oxide ester and polypropylene oxide ester, a polyalkylene oxide portion is, for example, a random copolymer or block copolymer of ethylene oxide and propylene oxide. A polyalkylene oxide ester compound which is a polymer is also preferably used.
[0091]
(D-4) The polyoxyalkylenealkylamine is generally used as a nonionic surfactant, and any conventionally known polyoxyalkylenealkylamine can be used without any limitation. As the (D-4) polyoxyalkylene alkylamine, for example, a compound represented by the general formula R ¹¹ N ｛(CH ₂ CH ₂ O) _j −H｝ ｛(CH ₂ CH ₂ O) _k And polyoxyethylene alkylamine represented by -H}. In the above general formula, R ¹¹ Is an alkyl or alkenyl group having 1 to 30 carbon atoms, preferably an alkyl group having 6 to 20 carbon atoms, and more preferably an alkyl group having 8 to 18 carbon atoms. Also, (CH ₂ CH ₂ J and k indicating the average chain length of the oxyethylene unit represented by O) may be the same or different, and each is in the range of 2 to 40, preferably 2 to 30, and more preferably 2 to 20. It is desirable that
[0092]
(D-5) Alkyldiethanolamine is generally used as a nonionic surfactant, and any conventionally known alkyldiethanolamine can be used without any limitation. (D-5) Alkyldiethanolamine represented by the general formula R ¹¹ N (CH ₂ CH ₂ OH) ₂ Are represented. In the above general formula, R ¹¹ Is as described above. Specific examples of (D-5) alkyldiethanolamine include lauryldiethanolamine, cetyldiethanolamine, stearyldiethanolamine, octyldiethanolamine, nonyldiethanolamine, sec-lauryldiethanolamine, and the like. Of these, lauryl diethanolamine is preferred.
[0093]
(D-6) The higher aliphatic amide is generally used as a nonionic surfactant, and any conventionally known higher aliphatic amide can be used without any limitation. (D-6) As a higher aliphatic amide, a compound represented by the general formula R ¹⁰ CON (CH ₂ CH ₂ OH) ₂ An alkyl diethanolamide represented by the following formula is preferably used. In the above general formula, R ¹⁰ Is as described above. (D-6) 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.
[0094]
Among the compounds (D) as described above, (D-1) a polyalkylene oxide, (D-2) an etherified product of a polyalkylene oxide, (D-3) a carboxylic acid ester of a polyalkylene oxide, and (D-4) ) Polyoxyalkylenealkylamines are preferably used.
[0095]
Further, (D) preferably has an average molecular weight in the range of usually 200 to 5,000. This average molecular weight is more preferably 250 or more, still more preferably 300 or more, even more preferably 350 or more, even more preferably 400 or more, particularly preferably 450 or more, and most preferably 500 or more. In addition, the average molecular weight is more preferably 4,000 or less, further preferably 3,000 or less, still more preferably 2,500 or less, even more preferably 2,000 or less, particularly Preferably it is less than 1,500, most preferably less than 1,000. If the average molecular weight is less than 200, the polymerization activity may be reduced and the bulk density of the obtained polymer may be reduced. When the average molecular weight exceeds 5,000, the viscosity of (D) becomes high and the solubility in a solvent becomes low, so that it may be difficult to supply the polymer to the polymerization reactor. Further, the bulk density of the obtained polymer may be reduced.
[0096]
In the method for producing a propylene polymer of the present invention, the polymerization or copolymerization of propylene is carried out using the polymerization catalyst comprising the above (A), (B) and (C) while supplying the above (D) to a polymerization reactor. Perform polymerization. The above (D) is supplied to the polymerization reactor from one or more arbitrary positions as a solution or slurry or as it is without using a solvent.
[0097]
The concentration of the (D) nonionic surfactant during the polymerization is supplied to the polymerization reactor such that the concentration is in the range of 0.1 to 100 mg per 1 kg of the reaction mixture in the polymerization system. When the concentration of (D) is less than 0.1 mg, fouling occurs or the bulk density of the obtained polymer decreases. On the other hand, if it is added in excess of 100 mg, no further effect can be expected on the suppression of fouling or the bulk density of the polymer, resulting in a decrease in polymerization activity. The preferred concentration range of (D) is 0.1 to 50.0 mg, more preferably 0.2 to 50 mg, further preferably 0.2 to 40 mg, still more preferably 0.3 to 30 mg, and particularly preferably. The range is from 0.4 to 25 mg, most preferably 0.5 to 20 mg.
[0098]
In the method for producing a propylene polymer of the present invention, any polymerization method can be adopted. Specific examples include bulk polymerization performed in a liquid olefin, solution polymerization and slurry polymerization performed in a liquid phase in the presence of an inert solvent, and gas phase polymerization performed in a gas phase monomer. Among these, bulk polymerization and gas phase polymerization are preferred, and bulk polymerization is particularly preferred.
[0099]
The polymerization temperature can be arbitrarily determined in consideration of the productivity and the molecular weight of the propylene polymer to be produced, but is usually in the range of 0 to 130 ° C., preferably in the range of 20 to 120 ° C. It is more preferably in the range of 40 to 100 ° C, particularly preferably in the range of 56 to 95 ° C, and most preferably in the range of 60 to 90 ° C. The pressure is generally in the range of normal pressure to 7.0 MPa in the polymerization in the liquid phase, and in the range of normal pressure to 5.0 MPa in the gas phase, and the properties and productivity of the propylene polymer to be obtained. An appropriate range can be selected in consideration of such factors. At the time of polymerization, the molecular weight can be adjusted by any means such as introduction of hydrogen, selection of temperature and pressure, and the like.
[0100]
During the polymerization, an organic metal compound such as an organic aluminum compound may be added to the polymerization reactor. As the organometallic compound, those similar to the above (C) can be used, and preferably, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, and tri-n-octylaluminum are exemplified. .
[0101]
The method for producing a propylene polymer of the present invention can be applied to both production of a propylene homopolymer and a propylene copolymer. The copolymer of propylene is propylene and ethylene or an α-olefin other than propylene, for example, 1-butene, 1-pentene, 1-hexene, 1-octene, 3-methyl-1-butene, 4-methyl-1- It is a copolymer with pentene, 1-decene, vinylcyclohexane, etc., and a small amount of vinyl aromatic compounds such as styrene, vinyltoluene and conjugated or non-conjugated dienes such as butadiene, isoprene, chloroprene and 1,4-hexadiene. It does not matter.
[0102]
When the propylene polymer produced by the present invention is a propylene homopolymer, its melting point Tm (° C.) is usually 143.0 ° C. or higher, preferably 144.0 ° C. or higher, more preferably 145.0 ° C. ° C or higher. According to the method of the present invention, it is possible to produce a propylene homopolymer in which the decrease in the melting point is suppressed as compared with the conventional method. The melting point of the propylene polymer can be measured by a differential scanning calorimeter.
[0103]
When the propylene polymer produced according to the present invention is a propylene copolymer, the propylene content Fp (mol%) is not particularly limited, but is usually preferably in the range of 80.0 to 99.5 mol%. , Preferably 90.0 to 99.0 mol%, more preferably 92.0 to 98.0 mol%, particularly preferably 93.0 to 97.5 mol%.
[0104]
Further, the method of the present invention is suitable for producing a propylene polymer in which the melting point Tm (° C.) and the propylene content Fp (mol%) of the propylene polymer satisfy the following formula (3). (4) It is more suitable for a method for producing a propylene polymer which more preferably satisfies the following formula (5).
[0105]
Tm ≧ 143.0−5.5 × (100−Fp) (3)
Tm ≧ 144.0-5.5 × (100-Fp) (4)
Tm ≧ 145.0−5.5 × (100−Fp) (5)
The propylene polymer obtained by the method of the present invention preferably has a bulk density of usually 0.30 g / ml or more, preferably 0.31 g / ml or more, more preferably 0.32 g / ml or more, and still more preferably. It has a bulk density of at least 0.33 g / ml, more preferably at least 0.34 g / ml, particularly preferably at least 0.35 g / ml, most preferably at least 0.36 g / ml.
[0106]
【Example】
Hereinafter, the present invention will be described further with reference to examples, but the present invention is not limited to these examples.
[0107]
The melting point (Tm) of the propylene polymer described herein is measured by the following method.
[0108]
Measurement of melting point (Tm)
Using a differential scanning calorimeter DCS7 manufactured by PERKIN-ELMER, the sample is first heated to 230 ° C. and held for 5 minutes, and then cooled to −30 ° C. at 20 ° C./min and held for 5 minutes. Thereafter, the melting peak when the temperature is raised again at 20 ° C./min is defined as the melting point.
[0109]
(A-1) Non-coordinating ion-containing compound
N, N-dimethylanilinium [4- (dichloromethylsilyl) -2,3,5,6-tetrafluorophenyl] tris (pentafluorophenyl) borate (a-1-1)
N, N-dimethylanilinium [4- (chlorodimethylsilyl) -2,3,5,6-tetrafluorophenyl] tris (pentafluorophenyl) borate (a-1-2)
Tri-n-butylammonium [(4-dichloromethylsilyl-2,3,5,6-tetrafluorophenyl)] tris (pentafluorophenyl) borate (a-1-3)
(A-2) Fine particle carrier
Silica (dried at 110 ° C. for 5 hours under a stream of nitrogen, hydroxyl content 4.4 mmol / g)
(B) Metallocene compound
Bis [2-methyl-4-phenyl- (η ⁵ -1-indenyl)] dimethylsilane zirconium dichloride (MPIZ)
Bis [2-methyl-4- (1-naphthyl)-(η ⁵ -1-indenyl)] dimethylsilane zirconium dichloride (MNIZ)
Bis [2-methyl-4,5-benzo- (η ⁵ -1-indenyl)] dimethylsilane zirconium dichloride (MBIZ)
(C) Organoaluminum compound
Triisobutylaluminum (TIBA)
Tri-n-octyl aluminum (TNOA)
(D-1)
Polyethylene glycol (Wako Pure Chemical Industries, average molecular weight 600: D-1-1) diol type polypropylene glycol (Wako Pure Chemical Industries, average molecular weight 700: D-1-2)
(D-2)
Polyethylene glycol monooleyl ether (manufactured by Tokyo Chemical Industry Co., Ltd., degree of polymerization of polyethylene glycol part: 10)
(D-3)
Polyethylene glycol monostearate (Tokyo Kasei Kogyo Co., Ltd., average degree of polymerization of polyethylene glycol part 4: D-3-1)
Polyethylene glycol monostearate (manufactured by Tokyo Chemical Industry Co., Ltd., average degree of polymerization of polyethylene glycol part 10: D-3-2)
Polyethylene glycol monolaurate, (Tokyo Kasei Kogyo Co., Ltd., average degree of polymerization of polyethylene glycol part 10: D-3-3)
(D-4)
Polyethylene glycol monostearylamine (Tokyo Kasei Kogyo Co., Ltd., average addition number of oxyethylene units 15: D-4-1)
Polyethylene glycol monostearylamine (manufactured by Tokyo Chemical Industry Co., Ltd., average addition number of oxyethylene units 10: D-4-2)
(D-5)
N-stearyl diethanolamine (manufactured by Tokyo Chemical Industry Co., Ltd.)
(D-6)
N-stearyl diethanolamide
(A) Preparation of a solid promoter component in which a non-coordinating ion-containing compound is chemically bonded to a fine particle carrier
(A-1)
A solution in which 0.3 g of (a-1-1) as a non-coordinating ion-containing compound is dissolved in 6 ml of dichloromethane, and 0.5 g of silica as fine particle carrier (a-2) in 30 ml of dichloromethane (110 ° C. under nitrogen stream) The slurry was added to the mixture, and the mixture was refluxed for 2 hours with stirring. Then, 3 ml of trimethylchlorosilane was added, and the mixture was refluxed for another 2 hours with stirring. Thereafter, the supernatant was removed and washed three times with 30 ml of dichloromethane to obtain a solid promoter component (A-1). The content of the non-coordinating ion-containing compound determined from the boron content was 0.12 mmol / g.
[0110]
(A-2) and (A-3)
In the production of the above (A-1), the same treatment was carried out except that (a-1-2) or (a-1-3) was used in place of (a-1-1) to obtain a solid support. Catalyst components (A-2) and (A-3) were obtained.
[0111]
Example 1
1) Preparation of polymerization catalyst
After collecting 20 mg of the component (A-1) in a dried and nitrogen-purged 30 ml flask, a hexane solution containing MBIZ as (B) and TIBA as (C) (0.5 mmol / L and 0.5 mol / L, respectively) L) was added and stirred at 30 ° C. for 10 minutes. Thereafter, 3 ml of dehydrated hexane was added to obtain a polymerization catalyst.
[0112]
2) Homopolymerization of propylene
1 ml of a 0.5 mol / L TIBA hexane solution and 3.0 mg of (D-1-1) as a nonionic surfactant were added to a 1.5 liter autoclave. Next, 8 mol of propylene was added, and after the temperature was raised to 60 ° C., the entire amount of the polymerization catalyst was injected into an autoclave. After polymerization for 30 minutes, unreacted propylene was removed to obtain a propylene polymer. No fouling was observed during the autoclave. Table 1 shows the results.
[0113]
Comparative Example 1
A propylene polymer was obtained by repeating the same operation as in Example 1 except that the component (D-1-1) was not used. Significant fouling was observed in the autoclave. In addition, the obtained polymer was bulky, and the bulk density could not be measured. Table 1 shows the results.
[0114]
Comparative Example 2
The same operation as in Example 1 was repeated except that cetyltrimethylammonium chloride (D-7), which is an ionic surfactant, was used instead of the component (D-1-1). Some fouling was observed during the autoclave. Table 1 shows the results.
[0115]
Comparative Example 3
The same operation was repeated except that (A-4) produced as described below was used as the solid promoter component in Example 1. Fouling was observed during the autoclave. Table 1 shows the results.
[0116]
Preparation of solid co-catalyst component (A-4)
In 30 ml of dichloromethane, 0.3 g of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate as a non-coordinating ion-containing compound and 0.5 g of silica as a fine particle carrier (a-2) (in a stream of nitrogen) (Dried at 110 ° C. for 5 hours) and stirred for 10 minutes. Dichloromethane was distilled off from the obtained slurry with stirring to obtain a solid promoter component (A-4).
[0117]
Comparative Example 4
The same operation as in Example 1 was repeated except that (A-5) silica-supported methylaluminoxane was used as the solid promoter component. Fouling was observed during the autoclave. Table 1 shows the results.
[0118]
Comparative Example 5
The same operation as in Example 1 was repeated except that component (D) was not added to the autoclave but was added during the preparation of the polymerization catalyst. Fouling was observed during the autoclave. Table 1 shows the results.
[0119]
Examples 2 to 4
The same procedure as in Example 1 was repeated except that the polymerization was carried out at 70 ° C. using the components shown in Table 1. No fouling was seen during the autoclave. Table 1 shows the results.
[0120]
Comparative Example 6
The same operation was repeated except that the component (D) was not used in Example 2. No fouling was seen during the autoclave. Table 1 shows the results.
[0121]
Example 5
The same operation as in Example 4 was repeated, except that (A-3) was used as the component (A) and the mixture was stirred at 50 ° C. for 60 minutes to prepare a polymerization catalyst. No fouling was seen during the autoclave. Table 1 shows the results.
[0122]
Example 6
1) Preparation of polymerization catalyst
After collecting 30 mg of the component (A-1) in a dried and nitrogen-purged 30 ml flask, a hexane solution containing MPIZ as (B) and TIBA as (C) (0.5 mmol / L and 0.5 mol / L, respectively) ) Was added and stirred at 30 ° C. for 10 minutes. Thereafter, 5.4 ml of a 0.07 mol / L TIBA-hexane solution was added to obtain a polymerization catalyst.
[0123]
2) Prepolymerization of propylene
A 100 ml eggplant-shaped flask with a three-way cock, which had been dried and purged with nitrogen, was purged with propylene gas. Next, while flowing nitrogen through the three-way cock, the entire amount of the polymerization catalyst prepared above was added from the three-way cock, and the mixture was stirred for 2 hours to perform preliminary polymerization.
[0124]
3) Homopolymerization of propylene
Using the entire amount of the prepolymerized catalyst prepared in 2) above, the same operation as in Example 1 was repeated except that the polymerization was carried out at 70 ° C., to obtain a propylene polymer. No fouling was seen during the autoclave. Table 1 shows the results.
[0125]
Examples 7 to 10
The same operation as in Example 6 was repeated, except that the components shown in Table 1 were used. No fouling was seen during the autoclave. Table 1 shows the results.
[0126]
Comparative Example 7
The same operation as in Example 9 was repeated, except that the amount of the component (D) was changed to the value shown in Table 1. No fouling was seen during the autoclave. Table 1 shows the results.
[0127]
Comparative Example 8
The same operation as in Example 6 was repeated except that the component (D) was not used. Significant fouling was seen during the autoclave. Table 1 shows the results.
[0128]
[Table 1]

[0129]
Example 11
1) Preparation of polymerization catalyst
After collecting 30 mg of the component (A-1) in a 30 ml flask which has been dried and purged with nitrogen, a hexane solution containing MNIZ as (B) and TNOA as (C) (0.5 mmol / L and 0.5 mol / L, respectively) ) Was added and stirred at 30 ° C. for 30 minutes. After cooling to room temperature, 5.4 ml of a 0.07 mol / L TIBA-hexane solution was added to obtain a polymerization catalyst.
[0130]
2) Prepolymerization of propylene
A 100 ml eggplant-shaped flask with a three-way cock, which had been dried and purged with nitrogen, was purged with propylene gas. Next, while flowing nitrogen through the three-way cock, the entire amount of the polymerization catalyst prepared above was added from the three-way cock, and the mixture was stirred at room temperature for 2 hours to perform preliminary polymerization.
[0131]
3) Copolymerization of propylene and ethylene
1 ml of a 0.5 mol / L TIBA-hexane solution, 1.0 mg of (D-1-1) as a component (D) and 8 mol of propylene were added to a 1.5 liter autoclave, and the temperature was raised to 65 ° C. Thereafter, the polymerization catalyst preliminarily polymerized in the above 2) (9 mg as the solid co-catalyst component (A)) was injected into the autoclave to start polymerization. One minute after the start of the polymerization, ethylene was introduced until its partial pressure became 0.25 MPa, and propylene and ethylene were copolymerized at 70 ° C. Fifteen minutes after the introduction of ethylene, the polymerization was stopped by injecting methanol. Unreacted propylene was removed to obtain a propylene copolymer. Table 2 shows the results.
[0132]
Examples 12 to 23
The same operation as in Example 11 was repeated except that the components shown in Table 2 were used, to obtain a propylene copolymer. Table 2 shows the results.
[0133]
Example 24
A propylene copolymer was obtained by repeating the same operation as in Example 11 except that the amount of MNIZ used was doubled. Table 2 shows the results.
[0134]
Comparative Example 9
A propylene copolymer was obtained by repeating the same operation as in Example 11 except that the amount of the component (D) was changed to the value shown in Table 2. Table 2 shows the results.
[0135]
Comparative Example 10
The same operation as in Example 16 was repeated except that the component (D) was not used, to obtain a propylene copolymer. Table 2 shows the results.
[0136]
Comparative Example 11
The same operation as in Example 21 was repeated except that the amount of the component (D) used was changed to the value shown in Table 2. Table 2 shows the results.
[0137]
Comparative Example 12
A propylene copolymer was obtained by repeating the same operation as in Example 11 except that cetyltrimethylammonium chloride (D-7) as an ionic surfactant was used as the component (D). Table 2 shows the results.
[0138]
Comparative Examples 13 and 14
The same operation as in Example 11 was repeated, except that (A-4) prepared in Comparative Example 3 or methylaluminoxane supported on silica (A-5) was used as the component (A), respectively. Table 2 shows the results.
[0139]
Comparative Example 15
Example 1 was repeated except that the component (D) was not added to the autoclave but was added during the preparation of the polymerization catalyst. Table 2 shows the results.
[0140]
[Table 2]

[0141]
【The invention's effect】
As described above, according to the present invention, even when a propylene copolymer is produced, without accompanying fouling, a polymer particle having a high bulk density can be obtained with high polymerization activity, and In the production of a propylene homopolymer, it is possible to obtain a propylene polymer in which a decrease in the melting point is suppressed.

Claims (6)

(D) Nonionic surface activity by a polymerization catalyst comprising (A) a solid co-catalyst component in which a non-coordinating ion-containing compound is chemically bonded on a fine particle carrier, (B) a metallocene compound and (C) an organometallic compound. A method for producing a propylene polymer, comprising supplying an agent to a polymerization reactor so as to be in a range of 0.1 to 100.0 mg per 1 kg of a polymerization reaction mixture in a polymerization system to polymerize or copolymerize propylene. The method according to claim 1, wherein the average molecular weight of (D) is in the range of 200 to 5,000. The method according to claim 1 or 2, wherein the propylene polymer is a copolymer of propylene. The method according to claim 1 or 2, wherein the propylene polymer is a propylene homopolymer having a melting point of 143.0 ° C or higher. The propylene polymer has the following formula (3)
Tm ≧ 143.0−5.5 × (100−Fp) (3)
(Where Tm and Fp represent the melting point (° C.) and the propylene content (mol%) of the propylene polymer, respectively)
The method according to claim 1, which satisfies the following. (A) is the following formula (1)
_{^{[M 1 (R 1) a}} (R 2) b (R 3) c (R 4 -L) d] - · [M 2 X e] + (1)
(Wherein M ¹ is a boron or aluminum atom, and R ¹ , R ² and R ³ may be the same or different and each independently represents a hydrocarbon or halogenated carbon having 1 to 20 carbon atoms. A hydrogen group, an alkoxy group, an aryloxy group or a halogen atom, R ⁴ is a hydrocarbon group having 1 to 20 carbon atoms and optionally containing a hetero atom, L is a silyl group, a hydroxyl group, a carboxyl group, Selected from an amino group, an alkoxy group, an aryloxy group, a phosphino group, and an alkyl group or an aryl group having at least one of these, a, b and c are 0 or an integer of 1 to 3, and d is 1 an to 4 integer, and a a + b + c + d = 4, [M 2 X e] + represents a monovalent cation, ^{M 2} is (e + 1) valent cation, X is any Ani A down, e is an integer of 0 or 1 to 3)
The method according to any one of claims 1 to 5, which is obtained by contacting the non-coordinating ion-containing compound (a-1) represented by the formula (1) with a particulate carrier (a-2).