JP2500262B2 - Method for producing liquid α-olefin copolymer - Google Patents

Method for producing liquid α-olefin copolymer

Info

Publication number
JP2500262B2
JP2500262B2 JP60059645A JP5964585A JP2500262B2 JP 2500262 B2 JP2500262 B2 JP 2500262B2 JP 60059645 A JP60059645 A JP 60059645A JP 5964585 A JP5964585 A JP 5964585A JP 2500262 B2 JP2500262 B2 JP 2500262B2
Authority
JP
Japan
Prior art keywords
cyclopentadienyl
bis
group
olefin copolymer
liquid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
JP60059645A
Other languages
Japanese (ja)
Other versions
JPS61221207A (en
Inventor
俊之 筒井
護 木岡
典夫 柏
Original Assignee
三井石油化学工業 株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 三井石油化学工業 株式会社 filed Critical 三井石油化学工業 株式会社
Priority to JP60059645A priority Critical patent/JP2500262B2/en
Priority to EP86302198A priority patent/EP0200351B2/en
Priority to US06/843,556 priority patent/US4704491A/en
Priority to DE8686302198T priority patent/DE3678024D1/en
Priority to CA000505067A priority patent/CA1263498A/en
Publication of JPS61221207A publication Critical patent/JPS61221207A/en
Application granted granted Critical
Publication of JP2500262B2 publication Critical patent/JP2500262B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/04—Reduction, e.g. hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65925—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually non-bridged

Description

【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、液状α−オレフイン共重合体の製法に関す
る。さらに、詳細には、均一性に優れ分子量分布が狭い
液状α−オレフイン共重合体の製法に関し、さらには、
該液状α−オレフイン共重合体を高活性触媒を用いて効
率的に製造する方法に関する。TECHNICAL FIELD The present invention relates to a method for producing a liquid α-olefin copolymer. More specifically, it relates to a method for producing a liquid α-olefin copolymer having excellent uniformity and a narrow molecular weight distribution, and further,
The present invention relates to a method for efficiently producing the liquid α-olefin copolymer using a highly active catalyst.

〔従来の技術〕[Conventional technology]

従来、水素の共存在下、チタン化合物又はバナジウム
化合物と有機アルミニウム化合物とから形成される触媒
を用いて液相中でエチレンと炭素数３以上のα−オレフ
インを共重合させることによつて液状の共重合体が得ら
れることは公知である。これらの方法のうちで、チタン
系触媒を使用する方法では重合活性は大きいが、一般に
得られた共重合体は分子量分布が広く、例えば潤滑油、
潤滑油添加剤あるいは燃料油添加剤等に用いる際、低粘
度品にあつては低分子量部をカツトしなければ高引火点
のものが得られず、また高粘度品にあつては流動点が高
すぎる為に実用に耐えないなどという欠点がある。他
方、バナジウム系触媒を使用する方法では、得られた共
重合体は分子量分布が狭く均一性に優れているが、一般
に重合活性が極めて小さいという欠点がある。Conventionally, in the presence of hydrogen in the liquid phase, a catalyst formed from a titanium compound or a vanadium compound and an organoaluminum compound is used to copolymerize ethylene and α-olefin having 3 or more carbon atoms in a liquid phase to obtain a liquid form. It is known that copolymers are obtained. Among these methods, a method using a titanium-based catalyst has a large polymerization activity, but generally the obtained copolymer has a wide molecular weight distribution, for example, a lubricating oil,
When used as a lubricating oil additive or fuel oil additive, a low-viscosity product cannot have a high flash point unless the low-molecular weight part is cut, and a high-viscosity product has a pour point. It has the drawback that it cannot be put to practical use because it is too expensive. On the other hand, in the method using a vanadium-based catalyst, the obtained copolymer has a narrow molecular weight distribution and is excellent in uniformity, but generally has a drawback that the polymerization activity is extremely small.

〔発明が解決しようとする問題点〕[Problems to be solved by the invention]

従つて、液状のα−オレフイン共重合体の製造に関す
る分野においては、重合活性に優れ、分子量分布が狭
く、均一性に優れている液状α−オレフイン共重合体を
効率的に製造することのできる方法が強く要望されてい
る。本発明者らは、液状α−オレフイン共重合体の製造
分野における先行技術が前述の状況下にあることを認識
し、重合活性に優れ、しかも分子量分布が狭く、均一性
に優れている液状α−オレフイン共重合体を製造するこ
とのできる方法を検討した結果、遷移金属化合物とアル
ミノオキサンからなる触媒の存在下に、少なくとも２種
以上のα−オレフインを共重合させることにより、前記
目的が達成できることを見出し、本発明に到達したもの
である。Therefore, in the field of producing a liquid α-olefin copolymer, it is possible to efficiently produce a liquid α-olefin copolymer having excellent polymerization activity, a narrow molecular weight distribution, and excellent uniformity. There is a strong demand for methods. The present inventors have recognized that the prior art in the field of producing liquid α-olefin copolymers is under the above-mentioned circumstances, and have excellent polymerization activity, and also have a narrow molecular weight distribution and excellent uniformity. -As a result of investigating a method capable of producing an olefin copolymer, the above-mentioned object is obtained by copolymerizing at least two kinds of α-olefins in the presence of a catalyst composed of a transition metal compound and aluminoxane. The inventors have reached the present invention by finding out what can be achieved.

〔問題点を解決するための手段〕及び〔作用〕 本発明は、 （Ａ）チタン、ジルコニウム、ハフニウム、バナジウム
からなる群より選ばれた遷移金属のシクロペンタジエニ
ル基を有する化合物、及び （Ｂ）アルミノオキサン、 からなる触媒の存在下に、炭素数が３ないし20のα−オ
レフィンから選ばれる少なくとも２種以上のα−オレフ
ィンを−50ないし200℃の温度で、共重合させることに
より極限粘土〔η〕が0.4dl/g以下であり、分子量分布
（▲▼／▲▼）が2.5以下であるα−オレフィ
ン共重合体を製造することを特徴とする液状α−オレフ
イン共重合体の製法を発明の要旨とするものである。[Means for Solving Problems] and [Action] The present invention provides (A) a compound having a cyclopentadienyl group of a transition metal selected from the group consisting of titanium, zirconium, hafnium and vanadium, and (B) ) In the presence of a catalyst comprising aluminoxane, at least two or more α-olefins selected from α-olefins having 3 to 20 carbon atoms are copolymerized at a temperature of -50 to 200 ° C to obtain an ultimate limit. A method for producing a liquid α-olefin copolymer, which comprises producing an α-olefin copolymer having a clay [η] of 0.4 dl / g or less and a molecular weight distribution (▲ ▼ / ▲ ▼) of 2.5 or less. Is the gist of the invention.

本発明の方法において使用される触媒構成成分の遷移
金属化合物（Ａ）は、チタン、ジルコニウム、ハフニウ
ム、バナジウムなの化合物を例示することができるがこ
れらの遷移金属化合物の中ではチタン又はジルコニウム
の化合物が好ましく、とくにジルコニウム化合物が高活
性であるので好ましい。該遷移金属化合物の好適な形態
としては、炭化水素基を有する化合物又は炭化水素基及
びハロゲン原子を有する化合物が好ましく、とりわけ、
好ましくは少なくとも１個、とくに好ましくは２個の炭
化水素基を有しかつ好ましくは少なくとも１個、特に好
ましくは２個のハロゲン原子を有する遷移金属化合物で
ある。炭化水素基として具体的には、メチル基、エチル
基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、
sec−ブチル基、tert−ブチル基、イソブチル基、ネオ
ペンチル基などのアルキル基、イソプロペニル基、１−
ブテニル基などのアルケニル基、シクロペンタジエニル
基、メチルシクロペンタジエニル基などのシクロアルカ
ジエニル基、ベンジル基、ネオフイル基などのアラルキ
ル基などを例示することができるが、これらの炭化水素
基のうちではシクロアルカジエニル基が好ましく、シク
ロペンタジエニル基がとくに好ましい。ハロゲン原子と
して具体的には、弗素、塩素、臭素、沃素原子を例示す
ることができる。さらに遷移金属化合物として具体的に
は、ビス（シクロペンタジエニル）ジメチルチタン、ビ
ス（シクロペンタジエニル）ジエチルチタン、ビス（シ
クロペンタジエニル）ジイソプロピルチタン、ビス（シ
クロペンタジエニル）ジメチルチタン、ビス（シクロペ
ンタジエニル）メチルチタンモノクロリド、ビス（シク
ロペンタジエニル）エチルチタンモノクロリド、ビス
（シクロペンタジエニル）イソプロピルチタンモノクロ
リド、ビス（シクロペンタジエニル）メチルチタンモノ
ブロミド、ビス（シクロペンタジエニル）メチルチタン
モノイオデイド、ビス（シクロペンタジエチル）チタン
ジフルオリド、ビス（シクロペンタジエニル）チタンジ
クロリド、ビス（シクロペンタジエニル）チタンジプロ
ミド、ビス（シクロペンタジエニル）チタンジイオデイ
ドなどのチタン化合物、ビス（シクロペンタジエニル）
ジメチルジルコニウム、ビス（シクロペンタジエニル）
ジエチルジルコニウム、ビス（メチルシクロペンタジエ
ニル）ジイソプロピルジルコニウム、ビス（シクロペン
タジエチル）メチルジルコニウムモノクロリド、ビス
（シクロペンタジエニル）エチルジルコニウムモノクロ
リド、ビス（シクロペンタジエニル）メチルジルコニウ
ムモノブロミド、ビス（シクロぺンタジエニル）メチル
ジルコニウムモノイオデイド、ビス（シクロペンタジエ
ニル）ジルコニウムジフルオリド、ビス（シクロペンタ
ジエニル）ジルコニウムジクロリド、ビス（シクロペン
タジエニル）ジルコニウムジブロミド、ビス（シクロペ
ンタジエニル）ジルコニウムモノクロリドモノハイドラ
イド、ビス（シクロペンタジエニル）ジルコニウムジイ
オデイドなどのジルコニウム化合物、ビス（シクロペン
タジエニル）ジメチルハフニウム、ビス（シクロペンタ
ジエニル）メチルハフニウムモノクロリド、ビス（シク
ロペンタジエニル）ハフニウムジクロリドなどのハフニ
ウム化合物、ビス（シクロペンタジエニル）バナジウム
ジクロリド、ビス（シクロペンタジエニル）バナジウム
モノクロリドなどのバナジウム化合物を例示することが
できる。Examples of the transition metal compound (A) which is a catalyst constituent component used in the method of the present invention include titanium, zirconium, hafnium and vanadium compounds. Among these transition metal compounds, the titanium or zirconium compound is A zirconium compound is preferable because it has high activity. As a suitable form of the transition metal compound, a compound having a hydrocarbon group or a compound having a hydrocarbon group and a halogen atom is preferable, and particularly,
Preference is given to transition metal compounds having at least 1, particularly preferably 2 hydrocarbon radicals and preferably at least 1, particularly preferably 2 halogen atoms. Specific examples of the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group,
sec-butyl group, tert-butyl group, isobutyl group, alkyl group such as neopentyl group, isopropenyl group, 1-
Examples thereof include an alkenyl group such as butenyl group, a cyclopentadienyl group, a cycloalkadienyl group such as methylcyclopentadienyl group, an aralkyl group such as benzyl group and neophyl group, and the like. Of these, a cycloalkadienyl group is preferable, and a cyclopentadienyl group is particularly preferable. Specific examples of the halogen atom include fluorine, chlorine, bromine and iodine atoms. Further, specific examples of the transition metal compound include bis (cyclopentadienyl) dimethyl titanium, bis (cyclopentadienyl) diethyl titanium, bis (cyclopentadienyl) diisopropyl titanium, bis (cyclopentadienyl) dimethyl titanium, Bis (cyclopentadienyl) methyl titanium monochloride, bis (cyclopentadienyl) ethyl titanium monochloride, bis (cyclopentadienyl) isopropyl titanium monochloride, bis (cyclopentadienyl) methyl titanium monobromide, bis ( Cyclopentadienyl) methyl titanium monoiodide, bis (cyclopentadienyl) titanium difluoride, bis (cyclopentadienyl) titanium dichloride, bis (cyclopentadienyl) titanium dipromide, bis (cyclopentadienyl) Titanium compounds such as Tanjiiodeido, bis (cyclopentadienyl)
Dimethylzirconium, bis (cyclopentadienyl)
Diethylzirconium, bis (methylcyclopentadienyl) diisopropylzirconium, bis (cyclopentadienyl) methylzirconium monochloride, bis (cyclopentadienyl) ethylzirconium monochloride, bis (cyclopentadienyl) methylzirconium monobromide, bis (Cyclopentadienyl) methylzirconium monoiodide, bis (cyclopentadienyl) zirconium difluoride, bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dibromide, bis (cyclopentadienyl) Zirconium monochloride monohydride, zirconium compounds such as bis (cyclopentadienyl) zirconium diiodide, bis (cyclopentadienyl) dimethyl Hafnium compounds such as hafnium, bis (cyclopentadienyl) methylhafnium monochloride, bis (cyclopentadienyl) hafnium dichloride, bis (cyclopentadienyl) vanadium dichloride, bis (cyclopentadienyl) vanadium monochloride, etc. A vanadium compound can be illustrated.

本発明の方法において使用される触媒構成成分のアル
ミノオキサン（Ｂ）として具体的には、一般式 （Ｉ）又は一般式〔II〕 （式中、Ｒは炭化水素基を示し、ｍは２以上の整数を
示す）で表わされる有機アルミニウム化合物を例示する
ことができる。該アルミノオキサンにおいて、Ｒはメチ
ル基、エチル基、プロピル基、ブチル基などの炭化水素
基であり、好ましくはメチル基、エチル基であり、特に
好ましくはメチル基である。ｍは２以上の整数、好まし
くは５以上、特に好ましくは10ないし100の整数であ
る。該アルミノオキサンの製造法としてたとえば次の方
法を例示することができる。Specific examples of the aluminoxane (B) as a catalyst constituent used in the method of the present invention include general formula (I) or general formula [II] (In the formula, R represents a hydrocarbon group and m represents an integer of 2 or more). In the aluminoxane, R is a hydrocarbon group such as a methyl group, an ethyl group, a propyl group and a butyl group, preferably a methyl group and an ethyl group, and particularly preferably a methyl group. m is an integer of 2 or more, preferably 5 or more, particularly preferably 10 to 100. The following method can be exemplified as a method for producing the aluminoxane.

（１）吸着水を含有する化合物、結晶水を含有する塩
類、例えば硫酸銅水和物、硫酸アルミニウム水和物など
の炭化水素媒体懸濁液にトリアルキルアルミニウムを添
加して反応させる方法。(1) A method in which a trialkylaluminum is added to a hydrocarbon medium suspension such as a compound containing adsorbed water or a salt containing water of crystallization, for example, copper sulfate hydrate or aluminum sulfate hydrate, and reacted.

（２）ベンゼン、トルエン、エチルエーテル、テトラヒ
ドロフランなどの媒体中でトリアルキルアルミニウムに
直接水を作用させる方法。これらの方法のうちでは
（１）の方法が好ましい。なお、該アルミノオキサンに
は他の成分、たとえば少量の有機金属成分を含んでいて
も差しつかえてない。(2) A method in which water is allowed to act directly on a trialkylaluminum in a medium such as benzene, toluene, ethyl ether, or tetrahydrofuran. Among these methods, the method (1) is preferable. It should be noted that the aluminoxane may contain other components, for example, a small amount of organometallic component, without any problem.

図１に本発明の方法において用いられる触媒の調整工
程を示す。本発明の方法において重合反応に供給される
α−オレフインとして具体的には、プロピレン、１−ブ
テン、１−へキセン、４−メチル−１−ペンテン、１−
オクテン、１−デセン、１−ドデセン、１−テトラデセ
ン、１−ヘキサデセン、１−オクタデセン、１−エイコ
センなどの炭素数が３ないし20のα−オレフィンを例示
することができ、これらの２種以上の混合オレフインが
重合原料として使用される。FIG. 1 shows a step of preparing a catalyst used in the method of the present invention. Specific examples of the α-olefin that is supplied to the polymerization reaction in the method of the present invention include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-
Examples of the α-olefin having 3 to 20 carbon atoms such as octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene can be exemplified, and two or more kinds of them can be used. Mixed olefins are used as polymerization raw materials.

本発明の方法において、α−オレフインの共重合反応
は炭化水素媒体中で実施される。炭化水素媒体として具
体的には、ブタン、イソブタン、ペンタン、ヘキサン、
オクタン、デカン、ドデカン、ヘキサデカン、オクタデ
カンなどの脂肪族系炭化水素、シクロペンタン、メチル
シクロペンタン、シクロヘキサン、シクロオクタンなど
の脂環族系炭化水素、ベンゼン、トルエン、キシレンな
どの芳香族系炭化水素、ガソリン、灯油、軽油などの石
油留分などの他に、原料のオレフインも炭化水素媒体と
なる。これらの炭化水素媒体の中で芳香族系炭化水素が
好ましい。In the method of the present invention, the α-olefin copolymerization reaction is carried out in a hydrocarbon medium. Specific examples of the hydrocarbon medium include butane, isobutane, pentane, hexane,
Octane, decane, dodecane, hexadecane, octadecane and other aliphatic hydrocarbons, cyclopentane, methylcyclopentane, cyclohexane, cyclooctane and other alicyclic hydrocarbons, benzene, toluene, xylene and other aromatic hydrocarbons, In addition to petroleum fractions such as gasoline, kerosene, and light oil, the raw material olefin is also a hydrocarbon medium. Of these hydrocarbon media, aromatic hydrocarbons are preferred.

本発明の方法においては、溶解重合法が通常採用され
る。重合反応の際の温度は通常は−50ないし200℃、好
ましくは−30ないし120℃の範囲である。In the method of the present invention, a solution polymerization method is usually adopted. The temperature during the polymerization reaction is usually in the range of -50 to 200 ° C, preferably -30 to 120 ° C.

本発明の方法を溶媒重合法で実施する際の該遷移金属
化合物の使用割合は、重合反応系内の遷移金属原子の濃
度として通常は10-8ないし10-2グラム原子/l、好ましく
は10-7ないし10-3グラム原子/lの範囲である。また、ア
ルミノオキサンの使用割合は、重合反応系内のアルミニ
ウム原子の濃度として通常は10-4ないし10-1グラム原子
/l、好ましくは10-3ないし５×10-2グラム原子/lの範囲
であり、また重合反応系内の遷移金属原子に対するアル
ミニウム原子の比として通常は４ないし、107、好まし
くは10ないし106の範囲である。共重合体の分子量は水
素及び／又は重合温度によつて調整することができる。The ratio of the transition metal compound used when carrying out the method of the present invention by a solvent polymerization method is usually 10 −8 to 10 −2 g atom / l, preferably 10 as the concentration of the transition metal atom in the polymerization reaction system. It is in the range of -7 to 10 -3 gram atom / l. The aluminoxane content is usually 10 -4 to 10 -1 gram atom as the concentration of aluminum atoms in the polymerization reaction system.
/ l, preferably in the range of 10 -3 to 5 × 10 -2 gram atom / l, and the ratio of aluminum atom to transition metal atom in the polymerization reaction system is usually 4 to 10 7 and preferably 10 to 10. It is in the range of 10 6 . The molecular weight of the copolymer can be adjusted by hydrogen and / or the polymerization temperature.

本発明の方法において、重合反応が終了した重合反応
混合物を常法によつて処理することにより、液状α−オ
レフイン共重合体が得られる。該液状α−オレフイン共
重合体は25℃において液状ないしは半固体状のオレフイ
ン共重合体であり、該液状α−オレフイン共重合体の13
5℃のデカリン中で測定した極限粘度〔η〕は0.4dl/g以
下の範囲であり、好ましくは0.005ないし0.4dl/g、とく
に好ましくは、0.01ないし0.3dl/gの範囲である。In the method of the present invention, a liquid α-olefin copolymer is obtained by treating the polymerization reaction mixture after completion of the polymerization reaction by a conventional method. The liquid α-olefin copolymer is a liquid or semi-solid olefin copolymer at 25 ° C.
The intrinsic viscosity [η] measured in decalin at 5 ° C is 0.4 dl / g or less, preferably 0.005 to 0.4 dl / g, and particularly preferably 0.01 to 0.3 dl / g.

該液状α−オレフイン共重合体のゲルパーミエイシヨ
ンクロマトグラフイー（GPC）によつて測定した分子量
分布は通常は３以下、好ましくは2.5以下である。The molecular weight distribution of the liquid α-olefin copolymer measured by gel permeation chromatography (GPC) is usually 3 or less, preferably 2.5 or less.

〔発明の効果〕〔The invention's effect〕

本発明の方法によれば、重合活性に優れ、分子量分布
が狭く、均一性に優れた液状α−オレフイン共重合体を
効率的に製造することができるという特徴がある。さら
には、水素非共存下においても液状α−オレフイン共重
合体を製造することができるという特徴があり、その結
果得られた該共重合体の分子鎖末端には不飽和結合が存
在し、その反応性を生かした機能性液状α−オレフイン
共重合体に変性し易いという特徴がある。The method of the present invention is characterized in that a liquid α-olefin copolymer having excellent polymerization activity, a narrow molecular weight distribution and excellent uniformity can be efficiently produced. Furthermore, there is a feature that a liquid α-olefin copolymer can be produced even in the absence of hydrogen, and as a result, an unsaturated bond exists at the molecular chain end of the copolymer, It is characterized in that it is easily modified into a functional liquid α-olefin copolymer that takes advantage of reactivity.

〔実施例〕〔Example〕

次に、本発明の方法を実施例によつて具体的に説明す
る。Next, the method of the present invention will be specifically described with reference to examples.

実施例１ アルミノオキサンの調製 充分にアルゴン置換した400mlのフラスコにAl2（S
O4）314H2O 37gとトルエン125mlを装入しスラリーとし
た。それに、トルエン125mlで希釈したトリメチルアル
ミニウム0.5molを０〜−５℃の温度下に滴下した。滴下
終了後、40℃まで昇温し、その温度で30時間反応させ
た。続いて、濾過により固液分離を行ない、更に、分離
液よりトルエンを除去し、白色固体のアルミノオキサン
15.2gを得た。ベンゼン中での凝固点降下により求めた
分子量は1600であり、アルミノオキサンのｍ値は26であ
つた。重合には、トルエンに再溶解して用いた。Example 1 Preparation of aluminoxane Al 2 (S
O 4) was charged with 3 14H 2 O 37 g and toluene 125ml was slurried. 0.5 mol of trimethylaluminum diluted with 125 ml of toluene was added dropwise thereto at a temperature of 0 to -5 ° C. After the dropping was completed, the temperature was raised to 40 ° C. and the reaction was carried out at that temperature for 30 hours. Then, solid-liquid separation is performed by filtration, and toluene is removed from the separated liquid to obtain a white solid aluminoxane.
15.2 g was obtained. The molecular weight determined by freezing point depression in benzene was 1600, and the a-value of aluminoxane was 26. In the polymerization, it was redissolved in toluene and used.

重合 充分に窒素置換した内容積2lのSUS製オートクレーブ
に精製トルエン500mlとプロピレン500mlを20℃で装入
し、引き続きアルミニウム原子換算で10ミリグラム原子
に相当する前記アルミノオキサン、ジルコニウム原子換
算で0.015ミリグラム原子に相当するトルエンに溶解し
たビス（シクロペンタジエニル）ジルコニウムジクロリ
ドを１−ヘキセン100mlと共に装入し、30℃で２時間重
合を行なった。少量のエタノールを添加することにより
重合を停止した後、未反応プロピレン及び１−ヘキセン
をパージした。ポリマーはトルエンに溶解していた。ポ
リマー溶液に塩酸水溶液を加え、触媒残渣を除去し、更
に水洗した後、トルエンを除去し乾燥を行なった。プロ
ピレン含量94モル％、〔η〕0.06dl/g、Mw/Mn 1.93であ
る液状ポリマーが52g得られた。なお、触媒の重合活性
は3500gポリマー／ミリグラム原子−Zrであった。Polymerization Charge 500 ml of purified toluene and 500 ml of propylene into an autoclave made of SUS with an internal volume of 2 l that has been sufficiently replaced with nitrogen at 20 ° C, and then continue to aluminoxane equivalent to 10 mg of aluminum atom equivalent, 0.015 mg of zirconium atom equivalent. Bis (cyclopentadienyl) zirconium dichloride dissolved in toluene corresponding to atoms was charged together with 100 ml of 1-hexene, and polymerization was carried out at 30 ° C. for 2 hours. After stopping the polymerization by adding a small amount of ethanol, unreacted propylene and 1-hexene were purged. The polymer was dissolved in toluene. Aqueous hydrochloric acid solution was added to the polymer solution to remove the catalyst residue, and after washing with water, toluene was removed and drying was performed. 52 g of a liquid polymer having a propylene content of 94 mol%, [η] 0.06 dl / g and Mw / Mn 1.93 was obtained. The polymerization activity of the catalyst was 3500 g polymer / milligram atom-Zr.

【図面の簡単な説明】[Brief description of drawings]

図１は、本発明の方法において用いられる触媒の調製工
程を示す説明図である。FIG. 1 is an explanatory view showing a preparation process of a catalyst used in the method of the present invention.

Claims (1)

(57)【特許請求の範囲】(57) [Claims] 【請求項１】（Ａ）チタン、ジルコニウム、ハフニウ
ム、バナジウムからなる群より選ばれた遷移金属のシク
ロペンタジエニル基を有する化合物、及び （Ｂ）アルミノオキサン、 からなる触媒の存在下に、炭素数が３ないし20のα−オ
レフィンから選ばれる少なくとも２種以上のα−オレフ
ィンを−50ないし200℃の温度で、共重合させることに
より極限粘度〔η〕が0.4dl/g以下であり、分子量分布
（▲▼／▲▼）が2.5以下であるα−オレフィ
ン共重合体を製造することを特徴とする液状α−オレフ
ィン共重合体の製法。1. In the presence of a catalyst comprising (A) a compound having a cyclopentadienyl group of a transition metal selected from the group consisting of titanium, zirconium, hafnium and vanadium, and (B) an aluminoxane, The intrinsic viscosity [η] is 0.4 dl / g or less by copolymerizing at least two or more α-olefins selected from α-olefins having 3 to 20 carbon atoms at a temperature of -50 to 200 ° C. A process for producing a liquid α-olefin copolymer, which comprises producing an α-olefin copolymer having a molecular weight distribution (▲ ▼ / ▲ ▼) of 2.5 or less.
JP60059645A 1985-03-26 1985-03-26 Method for producing liquid α-olefin copolymer Expired - Lifetime JP2500262B2 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
JP60059645A JP2500262B2 (en) 1985-03-26 1985-03-26 Method for producing liquid α-olefin copolymer
EP86302198A EP0200351B2 (en) 1985-03-26 1986-03-25 Liquid ethylene-type random copolymer, process for production thereof, and use thereof
US06/843,556 US4704491A (en) 1985-03-26 1986-03-25 Liquid ethylene-alpha-olefin random copolymer, process for production thereof, and use thereof
DE8686302198T DE3678024D1 (en) 1985-03-26 1986-03-25 LIQUID STATIC ETHYLENE COPOLYMER, METHOD FOR PRODUCING AND APPLYING THE SAME.
CA000505067A CA1263498A (en) 1985-03-26 1986-03-25 Liquid ethylene-type random copolymer, process for production thereof, and use thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP60059645A JP2500262B2 (en) 1985-03-26 1985-03-26 Method for producing liquid α-olefin copolymer

Publications (2)

Publication Number Publication Date
JPS61221207A JPS61221207A (en) 1986-10-01
JP2500262B2 true JP2500262B2 (en) 1996-05-29

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ID=13119157

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JP (1) JP2500262B2 (en)

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JP2000351813A (en) * 1999-04-09 2000-12-19 Mitsui Chemicals Inc ETHYLENE/alpha-OLEFIN COPOLYMER, ITS PRODUCTION, AND ITS USE
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KR101568186B1 (en) 2014-01-06 2015-11-11 대림산업 주식회사 Apparatus and method for polymerizing ethylene and alpha-olefin
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