JPH09176235A - Propylene polymerization method - Google Patents
Propylene polymerization methodInfo
- Publication number
- JPH09176235A JPH09176235A JP7336629A JP33662995A JPH09176235A JP H09176235 A JPH09176235 A JP H09176235A JP 7336629 A JP7336629 A JP 7336629A JP 33662995 A JP33662995 A JP 33662995A JP H09176235 A JPH09176235 A JP H09176235A
- Authority
- JP
- Japan
- Prior art keywords
- propylene
- catalyst
- polymerization method
- supercritical conditions
- under supercritical
- 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.)
- Pending
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
(57)【要約】
【課題】気相重合法における、触媒の装入に特殊な方法
が必要であるとか容積効率が悪いなどの問題、またこの
問題に対して塊状重合法と気相重合法を組み合わせた場
合の、連結の方法が複雑になるとか、不均一系の触媒を
用いるためにこの方法でも完全に不活性媒体を無くする
ことが困難であるという問題を解決して、効率良くポリ
プロピレンを製造する方法を提供する。
【解決手段】プロピレンに可溶な触媒、例えばメタロセ
ン触媒を溶解したプロピレンを超臨界条件下の反応帯域
に導入し超臨界条件下で重合反応することによりプロピ
レンを重合する。(57) 【Abstract】 PROBLEM TO BE SOLVED: In the gas phase polymerization method, there is a problem that a special method is required for charging a catalyst, volume efficiency is poor, and the bulk polymerization method and the gas phase polymerization method are used for this problem. In the case of combining the above, the problem of complicated coupling method, and the difficulty of completely eliminating the inert medium by this method due to the use of a heterogeneous catalyst is solved, and polypropylene is efficiently A method of manufacturing the is provided. SOLUTION: A propylene-soluble catalyst, for example, propylene in which a metallocene catalyst is dissolved is introduced into a reaction zone under supercritical conditions and a polymerization reaction is carried out under supercritical conditions to polymerize propylene.
Description
【０００１】[0001]
【発明の属する技術分野】本発明は新規なプロピレンの
重合方法に関する。詳しくは特定の触媒を用い、特定の
条件で重合する方法に関する。TECHNICAL FIELD The present invention relates to a novel propylene polymerization method. Specifically, it relates to a method of polymerizing under a specific condition using a specific catalyst.
【０００２】[0002]
【従来の技術】プロピレンの重合方法としては種々の方
法が知られており、不活性媒体の存在する溶媒重合法、
液状の単量体の存在下に行う塊状重合法、液状の媒体の
存在しない気相重合法が知られており、特に気相重合法
は液状の媒体が存在しないためポリマーの乾燥とか、単
量体の回収などが簡便であり優れた方法である。2. Description of the Related Art Various methods are known as a method for polymerizing propylene, including a solvent polymerization method in the presence of an inert medium,
Bulk polymerization method performed in the presence of a liquid monomer, a gas phase polymerization method in which a liquid medium does not exist is known. Particularly, since the gas phase polymerization method does not have a liquid medium, the polymer is dried or a single amount is used. It is an excellent method because it is easy to recover the body.
【０００３】[0003]
【発明が解決しようとする課題】気相重合法は上述のよ
うに優れた方法であるが難点としては触媒の装入に特殊
な方法が必要であるとか容積効率が悪いなどの問題があ
り、通常塊状重合法と組み合わせることが行われてい
る。しかしながらこの方法では塊状と気相を組み合わせ
るための連結の方法が複雑になるという問題があり、ま
た不均一系の触媒を用いるためにこの方法でも完全に不
活性媒体を無くすることが困難であるという問題があ
る。The gas phase polymerization method is an excellent method as described above, but there are problems such as the need for a special method for charging the catalyst and poor volumetric efficiency. Usually, the combination with the bulk polymerization method is performed. However, this method has a problem that the connecting method for combining the lump and the gas phase becomes complicated, and it is difficult to completely eliminate the inert medium by this method because a heterogeneous catalyst is used. There is a problem.
【０００４】本発明の目的は、上記問題を解決して効率
良くポリプロピレンを製造する方法を提供することにあ
る。An object of the present invention is to solve the above problems and provide a method for efficiently producing polypropylene.
【０００５】[0005]
【課題を解決するための手段】本発明者らは上記課題を
解決した重合方法について鋭意検討し本発明を完成し
た。Means for Solving the Problems The present inventors diligently studied a polymerization method which solved the above-mentioned problems and completed the present invention.
【０００６】即ち本発明は、プロピレンに可溶な触媒を
用いてプロピレンを重合する方法において、触媒を溶解
したプロピレンを超臨界条件下の反応帯域に導入し超臨
界条件下で重合反応することを特徴とするプロピレンの
重合方法である。That is, the present invention provides a method for polymerizing propylene using a catalyst soluble in propylene, in which propylene in which the catalyst is dissolved is introduced into a reaction zone under supercritical conditions and a polymerization reaction is carried out under supercritical conditions. It is a characteristic propylene polymerization method.
【０００７】[0007]
【発明の実施の形態】本発明において、プロピレンに可
溶な触媒としては、好ましくは、メタロセン系の化合物
あるいはそれと他の有機金属化合物、あるいは必要に応
じメタロセン系の化合物および／または有機金属化合物
と接触してアニオンを生成する化合物などからなるもの
が例示できる。BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the propylene-soluble catalyst is preferably a metallocene-based compound or a metallocene-based compound and / or another organometallic compound, or if necessary, a metallocene-based compound and / or an organometallic compound. An example is a compound formed of a compound that contacts with an anion.
【０００８】メタロセン系の触媒としては、W.Kaminsky
らによって報告されて以来（Angew.Chem.,97,507(198
5)）改良がなされており多くのメタロセン化合物と有機
金属化合物の組み合わせが知られている。As the metallocene catalyst, W. Kaminsky
(Angew. Chem., 97 , 507 (198
5)) Improvements have been made and many combinations of metallocene compounds and organometallic compounds are known.
【０００９】メタロセン化合物としては具体的には、Ｃ
2 対称性のアイソタクティックポリプロピレンを生成す
るものあるいは、ＣS 対称性のシンジオタクティックポ
リプロピレンを生成するものなどが代表的であるが、対
称性を有しないメタロセン化合物であっても有効な立体
規則性のポリプロピレンを与えるものであれば利用でき
る。このような化合物については、例えばチーグラー触
媒(Ziegler Catalysts) G.Finkら( Springer-Verlag Be
rlin) などに多くの例が報告されている。Specific examples of the metallocene compound include C
Or intended to produce a 2 symmetry of isotactic polypropylene, C S symmetry syndiotactic polypropylene such as those generated by the a representative, effective even no metallocene compound symmetry stereoregularity Any polypropylene can be used as long as it gives a good polypropylene. Such compounds are described, for example, in Ziegler Catalysts G. Fink et al. (Springer-Verlag Be
Many examples have been reported such as rlin).
【００１０】また通常希土類金属のメタロセン化合物以
外はアルミノキサンなどの有機金属化合物を併用する必
要があるが、併用される有機金属化合物としてはメチル
アルミノキサンなどのアルミノキサンの他に、通常のア
ルキルアルミニウム、アルキルリチウム、アルキルマグ
ネシウムなどの有機金属化合物とトリフェニルホウ素な
どのメタロセン化合物及び／又は有機金属化合物と反応
してアニオンとなるような化合物を組み合わせることも
可能であり、それらの具体例は上記文献あるいはそれに
引用された多くの総説ですでに良く知られている。In addition to the metallocene compounds of rare earth metals, it is usually necessary to use an organometallic compound such as an aluminoxane together. As the organometallic compound to be used in combination, in addition to an aluminoxane such as methylaluminoxane, an ordinary alkylaluminum, an alkyllithium are used. It is also possible to combine an organometallic compound such as alkylmagnesium with a metallocene compound such as triphenylboron and / or a compound capable of forming an anion by reacting with an organometallic compound, and specific examples thereof are cited in the above literature or cited therein. It is already well-known in many reviews.
【００１１】本発明において重要なのはメタロセン化合
物および有機金属化合物など併用する化合物として、使
用条件下において液状プロピレンに溶解するものを用い
ることにある。ここで使用条件下に液状プロピレンに溶
解するとは、触媒として各成分を別々に反応帯域に導入
する場合にはそれぞれの成分が液状プロピレンに溶解す
るということであり、また触媒成分を混合して導入する
場合には、混合したものが溶解しているということであ
る。What is important in the present invention is to use, as the compound used in combination with the metallocene compound and the organometallic compound, a compound which is soluble in liquid propylene under the conditions of use. Dissolving in liquid propylene under the conditions of use herein means that when each component is introduced separately into the reaction zone as a catalyst, each component is dissolved in liquid propylene, and the catalyst components are mixed and introduced. If so, it means that the mixture is dissolved.
【００１２】本発明において重要なのは反応帯域の条件
であり、反応帯域は超臨界条件下、即ち、プロピレンの
臨界温度（プロピレン単独の場合９２℃）より高温であ
り、しかも圧力は臨界圧力（プロピレン単独の場合４．
６２ＭＰａ）以上となる条件に保たれている必要があ
る。In the present invention, the conditions of the reaction zone are important, the reaction zone is under supercritical conditions, that is, higher than the critical temperature of propylene (92 ° C. in the case of propylene alone), and the pressure is the critical pressure (propylene alone). In case of 4.
62 MPa) or more.
【００１３】本発明において反応機の形状については特
に制限はないが、攪拌機を設けた槽形反応機、長い管状
の反応機などが利用できる。In the present invention, the shape of the reactor is not particularly limited, but a tank reactor provided with a stirrer, a long tubular reactor and the like can be used.
【００１４】本発明において触媒成分の装入方法として
は、各成分を別個に装入する方法、触媒成分の一部また
は全部を混合して装入する方法のどちらであっても良
い。ここで全成分を予め混合して装入する場合には、充
分に冷却した状態で混合するのが好ましい。In the present invention, the catalyst components may be charged either by charging each component separately or by mixing all or part of the catalyst components and charging them. When all the components are mixed and charged in advance, it is preferable to mix them in a sufficiently cooled state.
【００１５】[0015]
【実施例】以下に実施例を示し本発明をさらに説明す
る。The present invention will be further described with reference to the following examples.
【００１６】実施例１ 圧力を５０ｋｇ／ｃｍ2-Ｇに保つように設定された自動
弁を有する内容積５Ｌの攪拌機つきオートクレーブにプ
ロピレン１．５ｋｇを装入し攪拌しながら内温が９５℃
になるように昇温した。昇温の課程で自動弁が働き圧力
は５０ｋｇ／ｃｍ2-Ｇに保たれた。ただちに常法によっ
て合成したジメチルシランジイル−ｂｉｓ（２−メチル
−７−ナフチルインデニル）ジルコニウムジクロリドの
プロピレン溶液（０．１ｍｍｏｌ／Ｌ）とアルベマール
社製のメチルアルミノキサンをプロピレンに溶解した溶
液（１００ｍｍｏｌ／Ｌ）をそれぞれ２０ｍｌ圧入し
た。ついで９５℃で５０ｋｇ／ｃｍ2-Ｇとなるようにプ
ロピレンを圧入しながら３０分重合した。Example 1 1.5 kg of propylene was charged into an autoclave equipped with a stirrer and having an internal volume of 5 L, which had an automatic valve set to maintain the pressure at 50 kg / cm 2 -G, and the internal temperature was 95 ° C. while stirring.
The temperature was raised so that An automatic valve worked during the temperature rising process and the pressure was kept at 50 kg / cm 2 -G. A propylene solution (0.1 mmol / L) of dimethylsilanediyl-bis (2-methyl-7-naphthylindenyl) zirconium dichloride synthesized immediately by a conventional method and a solution of methylaluminoxane manufactured by Albemarle in propylene (100 mmol / 20 ml of each of L) was injected under pressure. Then, polymerization was carried out for 30 minutes while pressurizing propylene at 95 ° C. so that the pressure became 50 kg / cm 2 -G.
【００１７】重合後プロピレンをパージしながら冷却し
パウダーを取り出した。２３５ｇのパウダーが得られ、
パウダーは径が約３ｍｍの粒子状であり、嵩比重は０．
４２であった。また１３５℃のテトラリン溶液で測定し
た極限粘度数が０．５、示差走査熱量分析法で１０℃／
ｍｉｎで昇温して測定し吸熱ピークとして観測した融点
は１２６℃であった。After the polymerization, the propylene was cooled while purging, and the powder was taken out. 235g of powder is obtained,
The powder is in the form of particles having a diameter of about 3 mm and a bulk specific gravity of 0.
It was 42. Also, the intrinsic viscosity number measured with a tetralin solution at 135 ° C is 0.5, and the intrinsic viscosity is 10 ° C /
The melting point observed as an endothermic peak was 126 ° C. when the temperature was raised at min.
【００１８】[0018]
【発明の効果】本発明の方法を適用することによって効
率良くポリプロピレンを製造することができ工業的に極
めて価値がある。INDUSTRIAL APPLICABILITY By applying the method of the present invention, polypropylene can be efficiently produced and is industrially extremely valuable.
Claims (3)
ンを重合する方法において、触媒を溶解したプロピレン
を超臨界条件下の反応帯域に導入し超臨界条件下で重合
反応することを特徴とするプロピレンの重合方法。1. A method for polymerizing propylene using a catalyst soluble in propylene, characterized in that the catalyst-dissolved propylene is introduced into a reaction zone under supercritical conditions to carry out a polymerization reaction under supercritical conditions. Polymerization method of propylene.
である請求項１に記載の方法。2. The method according to claim 1, wherein the propylene-soluble catalyst is a metallocene catalyst.
載の方法。3. The method according to claim 1, wherein the reaction zone is 93 ° C. or higher.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7336629A JPH09176235A (en) | 1995-12-25 | 1995-12-25 | Propylene polymerization method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7336629A JPH09176235A (en) | 1995-12-25 | 1995-12-25 | Propylene polymerization method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09176235A true JPH09176235A (en) | 1997-07-08 |
Family
ID=18301140
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7336629A Pending JPH09176235A (en) | 1995-12-25 | 1995-12-25 | Propylene polymerization method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09176235A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006510796A (en) * | 2002-09-20 | 2006-03-30 | エクソンモービル・ケミカル・パテンツ・インク | Polymer production under supercritical conditions |
-
1995
- 1995-12-25 JP JP7336629A patent/JPH09176235A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006510796A (en) * | 2002-09-20 | 2006-03-30 | エクソンモービル・ケミカル・パテンツ・インク | Polymer production under supercritical conditions |
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